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classes/winter11/113BID24/Lecture Notes QM
classes/winter11/113BID24/Lecture Notes QM
Abstract
In these notes I present an overview of electrodynamics and quantum mechanics
which (together with statistical mechanics) are the foundation of much of today’s
technology: electronics, chemistry, communication, optics, etc.
CONTENTS
3
1
INTRODUCTION: THE UNITY OF SCIENCE
4
2
QUANTUM MECHANICS
Quantum mechanics (QM) is a theory of matter and its interactions with force fields
(here we will only care about electromagnetic fields). While classical mechanics and
electromagnetism are intuitive (one has a direct experience of gravitation, light, elec-
tricity, magnetism, etc.) quantum mechanics is not. The description of matter that arises
from the QM formalism is totally at odds with our daily experience: particles can pass
through walls, can be at two different places and in different states at the same time,
can behave as waves and interfere with each other. Worse, QM is a non-deterministic
description of reality: it only predicts the probability of observing events. This aspect
deeply disturbed Einstein who could not accept that QM was the correct final descrip-
tion of reality (as he famously quipped: ”God does not play dice”). He and many others
came up with alternative descriptions of QM introducing hidden variables (unknow-
able to the observer) to account for its non-deterministic aspects. But in 1964 John
Bell showed that if hidden variables existed some measurements would satisfy certain
inequalities. The experiments performed by Alain Aspect and his collaborators in the
1970’s showed that the Bell inequalities were violated as predicted by QM, but not by
the hidden variable theories thereby falsifying them.
Yet, for all its technical prowess Aspect’s experiment was only addressing a philo-
sophical issue concerning the foundations and interpretation of QM. The theory itself
had been amply vindicated earlier by its enormous predictive power: QM explains the
stability of atoms, their spectra, the origin of the star’s energy and of the elements and
their properties, the nature of the chemical bond, the origin of magnetism, conductivity,
superconductivity and superfluidity, the behaviour of semi-conductors and lasers, etc.,
etc.. All of today’s micro-electronic industry is derived from applications of QM (tran-
sistors, diodes, integrated circuits, etc.), the development of the chemical industry is a
result of the QM understanding of the chemical bond and the nuclear industry would of
course been impossible without an understanding of the nucleus and the nuclear forces
that QM provided.
So, for all its weirdness Quantum Mechanics is the most successfull explanation of
the World ever proposed by Mankind. It beats Platonicism, the Uppanishads, Kabbalah,
Scholasticism, etc., yet is non-intuitive and cannot be understood except by following
its mathematical formalism to its logical conclusions. ”The great book of Nature is
written in the language of mathematics”, Galileo’s quip is truer for QM more than for
any other scientific theory. More recently one of the founder’s of QM, Eugene Wigner
wrote in an article entitled ”the unreasonable effectiveness of mathematics in the natural
sciences”, that ”the miracle of the appropriateness of the language of mathematics for
the formulation of the laws of physics is a wonderful gift which we neither understand
nor deserve”.
5
6 QUANTUM MECHANICS
It is with this mind set that I would like you to approach the study of QM. Like an
apprentice sorcerer learning the tricks of his master without fully understanding them,
yet always at awe confronting their power. As we have done with electromagnetism,
we will approach QM by following as far as we can the historical narrative. We will
see why the radiation of a Black Body was such a puzzle that it prompted Max Plank to
introduce the idea that energy was quantized; why the stability of atoms and their spectra
prompted Bohr, Sommereld and others to suggest that the energy levels of atoms were
also quantized; how the idea that particles could also have wavelike behaviour was first
suggested by de Broglie and brought to fruition by Schroedinger, Heisenberg and Dirac.
And how from then on, QM revolutionized the understanding of matter, the chemical
bond, magnetism, conduction, etc.
F. 2.1. The emission spectrum in the visible range for a few elements. Notice the fine
spectral lines and the different spectral characteristics for the different elements.
This was one of the puzzles that QM solved.
(where κ is the compressibility and ρ the density of the medium), the electromagnetic
waves predicted by Maxwell and discovered by Hertz were assumed to propagate in
some continuum medium: the ether which properties determined their velocity. How-
ever all attempts to detect the ”wind” of ether resulting from the motion of the Earth in
that medium proved negative. This prompted Einstein to formulate his theory of rela-
tivity which postulated the constancy of the speed of light and got rid of any notion of
ether, see Appendix.
Then there were questions related to the emission and absorption spectra of elements
that exhibited discrete lines rather than an undifferentiated continuum of absorption or
emission, as was the case for sound and water waves and as we have seen for scattered
and refracted light. Not only did the elements exhibit specific adsorption lines but those
differed from element to element. These observations did not fit with the then prevailing
conception of matter as a continuum.
Finally there was the problem of the radiation from a Black Body, a material (such as
to a good approximation graphite) which adsorbs radiation uniformly at all frequencies
and which can therefore also emit radiation uniformly at all frequencies. Notice how-
ever that many bodies (e.g. the elements just mentioned) are not black-bodies as they
adsorb/emit only at certain frequencies. At a given temperature, the radiation inside a
black body cavity is at thermal equilibrium with the walls of the cavity that absorb and
re-emit it. When computing the electromagnetic radiation energy emitted by a black-
body at a given temperature, one found its energy to diverge because the number of
modes at high frequencies diverged. This was not only absurd but also in contradiction
8 QUANTUM MECHANICS
with the experiments which studied the energy distribution inside the cavity by measur-
ing the energy leaking out of the cavity (for example through a small hole) as a function
of frequency.
To see how this comes about, consider a square cavity (an oven) of size a at tempera-
ture T . As we have seen, a body at a given temperature emits electromagnetic radiation,
see Fig.??. Imagine that the walls of the cavity are made of small oscillators emitting ra-
diation at frequency ω (like the oscillators we considered when studying the frequency
dependence of the refraction index). Stationary waves of the form sin ~k · ~r cos ωt will
be present in the cavity if its walls are reflecting (though for the energy to equilibrate
between oscillators the walls cannot be 100% reflective). To satisfy the boundary con-
ditions on the walls we shall require that: k x = πl/a, ky = πm/a, kz = πn/a (n, m, l ≥ 0).
Hence we have: k2 = (l2 + m2 + n2 )(π/a)2 ≡ (πρ/a)2 . The number of modes dNlnm with
such wavelength is:
4πρ2 ka adk k dk
dNlnm = 2 dρ= π( )2 = 8πa3 ( )2
8 π π 2π 2π
The factor 2 results from the two possible polarizations of the fields, while the factor
(4πρ2 /8)dρ counts the number of modes in a shell in the positive octant (n, m, l ≥ 0).
According to the equipartition theorem of statistical mechanics (see below) the average
energy of each oscillatory mode is: < E >= kB T . Using the relations: k = ω/c ≡ 2πν/c
(ν like f is the frequency), the energy density of the emitted radiation du = dNlnm <
E > /a3 becomes:
8πkB T 2
du = ν dν (2.1)
c3
hence the total energy, the integral of the energy density over all frequencies, diverges as
ν3 . This divergence became known as the Jeans’ (or ultra-violet) catastrophy. While the
data agreed with that formula at low frequencies, it differed at high frequencies (small
wavelengths).
, so that light of energy En is made up of n quantas: En = nhν. In that case the average
energy emitted at frequency ν is the sum over all possible energies En , weighted by their
Boltzmann probability (see below the Chapter on Statistical Mechanics):
e−En /kB T
P(En ) = P −E /k T
ne
n B
X hν
< E >= En P(En ) =
n
ehν/kB T − 1
When hν kB T , one recovers the previous result: < E >= kB T , however at large
emission frequencies the average energy decays as < E >∼ hν exp(−hν/kB T ). Planck
therefore suggested to modify the previous result, Eq.2.1 to yield, see Fig.2.2:
8πhν3 1
ρ(ν) ≡ du/dν = (2.2)
c3 ehν/kB T − 1
Where ρ(ν) is known as the spectral density of radiation. Identifying the smallest quanta
of energy with a light particle (a photon of energy hν), Eq.2.2 states that the density of
photons in a Black-body is:
dN p ρ(ν) 8πν2 1
= = 3 hν/k T (2.3)
dν hν c e B −1
Notice that the total energy density in the cavity is now finite:
8π5 k4B 4
Z ∞
8π(kB T )4 ∞ x3
Z
Utot = ρ(ν)dν = 3 3
dx x = T (2.4)
0 hc 0 e − 1 15h3 c3
R∞
Where we used the equality: 0 dx x3 /(e x − 1) = π4 /15. The total radiated power per
unit area trough a small hole in the cavity becomes,
cUtot 1
Z Z
cUtot
Irad = k̂ · n̂dΩ = cos θd(cos θ) = σS B T 4 (2.5)
4π 2 0
F. 2.2. The emission spectra of the sun and the universe. The sun emission spectra is
pretty well fit by the spectrum of a lack body at 5770K, however notice the existence
of some specific adsorption bands in the visible and UV spectrum. The universe on
the other hand presents a spectrum that is perfectly matched by a black-body at
2.726K.
at thermal equilibrium with the reacting nuclear particles and diffuse out to the Sun’s
surface which is much cooler. By fitting the spectrum of the sunlight to Planck’s for-
mula one can determine the Sun’s surface temperature: T S = 5770K. The total power
generated at the Sun’s core and emitted at its surface is:
where RS = 6.96 108 m is the Sun’s radius. Since the radius of the Sun’s core is es-
timated to be ∼ RS /5 the volume of the core is: Vcore = 1.13 1025 m3 and the average
power per unit volume generated in the Sun’s core is: PS /Vcore = 34 W/m3 . This is less
than the power generated by our body to keep warm!!
There are a few ways to verify that. Let us assume an average daily calory intake of '
3000kcal ' 1.2 107 J, which comes to a power consumption of ' 150W. Approximating
a man as a cylinder of height L = 2m and radius r = 0.2m, the power consumption per
unit volume is ' 600 W/m3 of which about half goes to metabolic activity. Alternatively
one can use Stefan’s law to estimate the losses between a body at 37◦ C (T b = 310◦ K)
and an environment at 27◦ C (T e = 300◦ K) (this is a crude estimate since other effects
such as perspiration regulate our temperature): ∆I = σS B (T b4 − T e4 ) ' 64W/m2 which
yields a power per unit volume ' 640W/m3 . From these consistent estimates we de-
duce that our power consumption per unit volume is much larger than the Sun’s!! What
makes the Sun so bright and hot is its huge mass, not its rather inefficient thermonuclear
reactions.
Let us now estimate the temperature of the Earth T E resulting from its adsorption of
THE PUZZLES OF MATTER AND RADIATION 11
the Sun’s radiation and its own radiation at T E . The sunlight impinging on the Earth at
a distance from the Sun RS E = 1.496 1011 m has an intensity:
Of that radiation a fraction (known as the Earth’s albedo) α ∼30% is reflected, mostly
by the clouds, snow and ice-caps. The Sun radiation power arriving at the surface of the
Earth is thus about 1 kW/m2 . It is an important number to remember when designing
solar energy plants: its sets the maximal power per unit area available from the Sun.
Notice that by measuring the radiation arriving on Earth and the angle sustained by
the Sun: θS = (RS /RS E ) one can also get an estimate of the Sun’s temperature: T S =
(IE /σS B θS2 )1/4 . The energy absorbed by the Earth heats it and is reradiated (to a good
approximation) like a black body at temperature T E . We can compute the temperature
of the Earth by a simple energy balance. At steady-state the energy radiated is equal to
the energy absorbed:
σS B T E4 4πR2E = (1 − α)IE πR2E
From which we get T E = ((1 − α)IE /4σS B )1/4 = 255K = -18C. The Earth is actually
slightly warmer because of the green house effect that reflects part of the emitted energy
back to Earth.
by the expansion factor αe = a0 /a. So that the energy density du0 of the background
photons at frequency ν0 obeys now:
8πν2 1
(a0 )3 du0 = hν0 a3 dN p = hν0 a3 3 hν/k T −1
dν
c e B
02
0 3 8πν 1
= (a0 )3 α−3
e hν αe dν0 (2.6)
c3 ehν0 /kB (T/αe ) − 1
which is the energy density of a black-body at a temperature T 0 , smaller than the tem-
perature at decoupling T by the expansion factor αe : T 0 = (T/αe ):
8πhν0 3 1
du0 = 3 hν 0 /k T 0 dν0
c e B −1
Because the Universe expanded by a factor αe ∼ 1100 since the decoupling time, one
obtains a current temperature for the background radiation of T 0 = 2.72◦ K. The precise
agreement on the value of that temperature is not very important as is the observation
that the cosmic background radiation is the best Black-Body ever observed. It is also
highly isotropic in the rest frame of the Universe. As our galaxy the Milky Way moves
at about 600 km/sec with respect to the Cosmic background, the Doppler effect red-
shifts the radiation in one direction and blue-shifts it in the opposite one. This effect can
be subtracted from the measured distribution of radiation intensities. One also needs to
subtract the contribution from the stars in the galaxy (which fortunately emit at much
higher frequencies, in the visible mostly). The measured variations in the temperature of
the Universe at different angular positions are then smaller than 10−5 K, yet these small
fluctuations served as the nucleation points for the galaxies and can account for their
observed distribution, see Fig.2.3. As E.Wigner wrote it is a ”miracle ... that we neither
undersand nor deserve” that a theory devised to explain (approximatively) the radia-
tion of hot bodies has turned out to provide such an amazingly precise and powerfull
description of the Universe!
2.1.2 The photo-electric effect
Besides the emission spectrum of atoms and the black body radiation, an other ex-
periment stood in apparent contradiction with Maxwell’s electromagnetic theory: the
photo-electric effect which observed that electron were emitted from a conducting ma-
terial with an energy that depended on the color (the frequency) of the radiation not on
its intensity. This was at odds with Maxwell’s electromagnetic theory that asserted that
the energy of radiation was related to its intensity (see Eq.??) not its frequency! Ein-
stein knew the solution for Black-body radiation for which Planck had to assume that
the radiation emitters in the walls’ cavity could only emit light in small quantas. In 1905
Einstein went further and assumed that all light actually comes in small bunches, pho-
tons, which energy is proportional to their frequency: E = hν. When such a photon is
absorbed by an electron its energy is used to tear the electron from the binding potential
Φ of the material and move it at velocity v:
1 2
hν = mv + Φ (2.7)
2
THE PUZZLES OF MATTER AND RADIATION 13
F. 2.3. The temperature of the cosmic microwave background measured across the
sky by the COsmic Background Explorer (COBE) satellite. The top image is the
raw data which is red/blue shifted due to the movement of our galaxy through the
universe at ∼ 600km/s. Correcting for this Doppler shift yields the middle image
which is still ”polluted” at the equator by the light emitted from the stars in our
galaxy. Substracting that measurable emission yields the bottom image where the
temperature fluctuations of the microwave background across the Universe are as
small as 10µ◦ K. These small fluctuations nonetheless served as nucleation points
for the formation of the stars and galaxies shortly after the decoupling time.
Hence an electron can only be observed if light of high enough frequency is used to
remove it from the material. The kinetic energy of the electron increases then linearly
with the illumination frequency. The current emitted is however proportional to the
number of adsorbed photons, i.e. to the light intensity. At the time Einstein proposal
was revolutionary since it assumed that energy came in discrete packets that could not be
infinitely divided and it appeared to contradict Maxwell’s equations. It took 16 years and
confirming experiments to establish the validity of his model, for which he got the Nobel
prize in 1921 (and not for his more profound and revolutionary theories of relativity
and gravitation). Incidently from Einstein’s relation between energy and momentum:
E 2 = (mc2 )2 + (pc)2 (see Appendix) one deduces that if the energy of the photon (of
mass m = 0) is quantized so must its momentum be: p = E/c = h/λ ≡ ~k (~ ≡ h/2π).
14 QUANTUM MECHANICS
m= 2 3 4 5 6 7 8
Lyman series (n=1) 121.6 102.6 97.2 94.9 93.7 93.0 92.6
Balmer series (n=2) - 656.3 486.1 434.1 410.2 397.0 388.9
Pashen series (n=3) - - 1870 1280 1090 1000 954
Table 2.1 The major emission lines in the hydrogen atom. The wavelength (in nm) is
tabulated for various values of the initial (m) and final state (n)
Bohr’s approach to the hydrogen atom was generalized in 1915 by Arnold Som-
merfeld who proposed that for any bound particle (atom, harmonic oscillator, etc.) a
quantity known in classical mechanics as the action was quantized:
I
~p · d~q = nh (2.10)
where ~p, ~q are the momentum and coordinate of the particle. The Wilson-Sommerfeld
quantization rule, Eq.2.10, reduces to Bohr’s quantization of the angular momentum in
the case of the hydrogen atom since the integral pdq = 2πmvr. But the same rule also
H
explains why the oscillators of frequency ω assumed by Planck to exist in the walls of
a back-body would emit√ radiation in quantas of energy ~ω. For a harmonic oscillator
with frequency ω = k/m, the energy is:
p2 kq2 p2 mω2 q2
Eosc = + = +
2m 2 2m 2
from which one derives:
I Z qm q Z qm q
pdq = 2 2mEosc − (mωq)2 = 2mω q2m − q2 dq = πmωq2m
−qm −qm
with q2m ≡ 2Eosc /mω2 . Hence Eq.2.10 implies: Eosc = n~ω, which is the assumption
made by Planck.
The Wilson-Sommerfeld quantization rule can also be used to find the energy level
of a quantum rotator rotating at frequency ω about one of its major axes with moment
of inertia I . In that case the angular moment Iω = l~ (l = 0, 1, 2, ...) and the angular
energy is El = Iω2 /2 = ~2 l2 /2I.
In 1924, Louis de Broglie (in his Ph.D thesis!) generalizing Sommerfeld’s idea sug-
gested that all matter are described by waves. So, just as a photon possesses a momen-
tum p = ~k, thus an electron is characterized by wavevector: k = p/~. The Wilson-
Sommerfeld rule is thus equivalent to the requirement that the electron wave in a bound
system interfers constructively to form a standing wave. As we shall see in the following
de Broglie’s analogy opened the way for the formal development of quantum mechan-
ics from its analogy with optics: classical mechanics becoming to quantum mechanics
what geometrical optics is to electromagnetic waves.
16 QUANTUM MECHANICS
F. 2.4. (A) The absorption of radiation by an atom in its ground state. (B) the stimu-
lated emission of a photon in presence of radiation by an atom in its excited state:
notice that this process is the time reversal of adsorption. (C) The spontaneous emis-
sion of a photon (in absence of radiation) by an atom in its excited state.
c3 λ3
B12 = =
8πhν τ s 8πhτ s
3
Einstein model could account for Planck’s Black-body radiation if atoms capable
of absorbing radiation at all frequencies are uniformly present. It also made possible
decades later the invention of the laser, acronym for Light Amplification by Stimulated
Emission of Radiation. A laser consists of a light amplifying medium inside a highly
reflective optical cavity, which usually consists of two mirrors arranged such that light
bounces back and forth, each time passing through the gain medium, see Fig.2.5. Typi-
cally one of the two mirrors is partially transparent to let part of the beam exit the cavity.
To achieve light amplification the excited state in the medium of a laser cavity emitting
at frequency ν0 = ∆E/h has to be more populated than the lower energy state. Since at
thermodynamic equilibrium low energy states are always more populated than higher
energy ones, energy must be injected in the medium to ”pump” (i.e. excite) atoms from
the ground state into the light emitting state.
Let us therefore consider light of intensity I(z, ν) = ρ(z, ν)c (0 < z < l) propagating
in a cavity of length l and cross section S . Due to stimulated emission of power dPemit
in a volume dV = S dz the increase in the light intensity is:
18 QUANTUM MECHANICS
dI
= dPemit /dV = hν0 (n2 − n1 )B12 ρ(ν)δ(ν − ν0 )
dz
c2
= (n2 − n1 ) I(z, ν)δ(ν − ν0 ) (2.11)
8πν02 τ s
For various reasons that we shall discuss later, the transition frequency between two
R the δ-function in the preceeding equation
states is never infintely sharp and one replaces
by a function g(ν) which approximates it: g(ν)dν = 1. Quite often the response g(ν)
of a resonant oscillator is appropriate (see Appendix on Fourier transforms):
γ/π
g(ν) =
(ν − ν0 )2 + γ2
One then obtains:
dI c2
= (n2 − n1 ) g(ν)I(z, ν) ≡ γ(ν)I(z, ν)
dz 8πν02 τ s
As argued above, the light intensity grows exponentially when the population of atoms
in the medium is inverted, i.e. when n2 > n1 . As light propagates in the cavity it suffer
losses (due to adsorption for example) of magnitude α cm−1 . Since light has to come
out of the cavity there are also losses due to the fact that only a portion R of the intensity
is reflected back into the cavity. For a laser to operate the losses must equal the gain:
R exp[(γ(ν) − α)l] = 1, which imply that the population inversion at threshold has to
satisfy:
8πτ s 1
(n2 − n1 )t = 2 (α − ln R)
λ g(ν) l
Hence the longer the wavelength the smaller the required population inversion for las-
ing. That is one of the reasons that masers (lasers in the microwave range) were the
first to be invented while X-ray lasers, even though of great utility, have been difficult
to develop. During steady-state laser operation the balance of losses and gain imply that
the population inversion remains at threshold. The more the ground state is pumped, the
more the excited state is induced to emit by the increased light density in the cavity, thus
keeping the difference between the density of the two states fixed at its threshold.
QUANTUM MECHANICAL FORMALISM 19
According to Dirac, a physical system is characterized by its state |Ψ > (also called
wave-function by Schroedinger). These states are complex unit vectors in a so-called
Hilbert space, defined so that their scalar product < Ψ|Ψ >= 1. When an observable
O is measured, the system is perturbed and ends up in an eigenstate |n > of O with
eigenvalue On : O|n >= On |n > (in linear algebra the eigenstates are the vectors that
diagonalize the matrix O). As in linear algebra one can expressing the vector-state |Ψ >
in terms of the eigenvectors |n > of O:
X
|Ψ >= αn |n > (2.12)
n
Since |Ψ > is a complex vector its conjugate is: < Ψ| = n α∗n < n|. The physical
P
interpretation of the amplitudes αn is at the core of Dirac’s formulation: the probability
of observing a system in state |n > after the measurement of O is: |αn |2 . So that the
probability of measuring a value On when the system is in state |Ψ > is:
Notice that |Ψ > being a unit vector: n |αn |2 = 1 as it should for |αn |2 to be interpreted
P
as a probability. This is the physical interpretation of the wave-function and the intrinsic
indeterminism of QM that so annoyed Einstein. The average value of O in state |Ψ > is:
X
< Ψ|O|Ψ > = (< n|α∗ n )O(αm |m >)
n,m
X
= Om α∗ n αm < n|m > (2.14)
n,m
X X
= |αn |2 On = P(On )On =< O > (2.15)
n n
where we assumed the eigenstates to be orthonormal < n|m >= δnm . Quantum me-
chanics in Dirac’s formulation is thus reduced to linear algebra: the states are complex
vectors and the observables complex matrices with real eigenvalues, i.e. Hermitian ma-
trices satisfying Amn = A∗nm . If the eigenstates of one operator (observable) A are also
the eigenstates of an other operator B then A and B commute:
AB|n >= Abn |n >= an bn |n >= bn an |n >= bn A|n >= BA|n >
If the operators commute they can be both measured simultaneously: they are diagonal-
ized by (i.e they share) the same eigenstates. If on the other hand the eigenstates of A
and B are not identical, their simultaneous measurement is not possible. Let {|n >} be
the eigenvectors of A, then
X X
BA|n >= Ban |n >= an B|n >= an |m >< m|B|n >= an Bmn |m >
m m
hence the operators do not commute [A, B] ≡ AB − BA , 0. We shall see later that
the non-commutability of operators (which is quite common with matrix operations)
is at the core of Heisenberg uncertainty principle which states that the position and
momentum of a particle cannot be simultaneously determined.
The energy being an important observable in physics, the energy operator (or Hamil-
tonian, H) plays an important role in Quantum Mechanics. Its eigenvalues are the pos-
sible measured energies of the system (which can be discrete or continuous) and its
eigenmodes are like the resonant modes of an oscillator or the specific orbits of the
electron in Bohr’s atom:
H|n >= n |n >
From Planck and Einstein, we know that there is a relation between energy and fre-
quency: n = ~ωn , so that an eigenstate with given frequency ωn evolves in time as
exp(−iωn t) = exp(−in t/~). Notice that if the initial state of the system is one of the
SIMPLE QM SYSTEMS 21
eigenstates |n >, it remains there with probability P = | exp(−iωn t)|2 = 1. If however the
initial state is |Ψ(0) >= n αn |n > then:
P
X
|Ψ(t) >= αn e−in t/~t |n >
n
∂ 1 X 1
|Ψ(t) >= αn n e−in t/~t |n >= H|Ψ(t) >
∂t i~ n i~
F. 2.6. The chiral amonia molecule, NHDT consist of a nitrogen atom bound to the
different isotopes of hydrogen(H): deuterium(D) and tritium(T). This molecule exist
with different chirality: left-handed or right-handed which are mirror images of each
other. Since nitrogen is slightly more electrophilic (negatively charged) than the
hydrogen isotopes the molecule possesses a small electric dipole moment µ.
0
Its eigenvalues (eigen-energies) are: E I,II = E0 ± A and its eigenvectors are:
! !
1 1
|I >= √1 |II >= √1
2 −1 2 1
F. 2.7. The gedanken (thought) experiment that Schroedinger proposed to test the va-
lidity of QM. In a closed box isolated from the external world there is a cat and a
radioactive source of say β−particles (electrons). If a particle is emitted and detected
by a Geiger counter a poison vial is broken that kills the cat. Otherwise the cat is
alive. As the state of the particle is a superposition of bound and emitted particle,
one must consider the cat to be in a superposition of a live and dead animal. For Ein-
stein that thought experiment demonstrated that QM was incomplete since it gave
rise to absurd assumptions. Yet, when isolated from the external world (a tall order
for macroscopic systems) all experiments so far are consistent with this ”absurd”
superposition of states.
So did Einstein ask: how was the cat ”really” before we looked into the box? He
claimed that the superposition is non-sensical and the cat is either dead or alive. He then
argued that some unknown factors (hidden variables) in the description of the micro-
scopic two-state sytem that determines the cat’s observed state results in the QM proba-
bilistic and verified predictions. However as mentioned earlier, the experimental viola-
tion of Bells’ inequalities suggest that Einstein was wrong and that such ”Schroedinger
cats” exist as a superposition of dead and alive states, even if we have no clue what that
means! We will discuss again that point more quantitatively below.
A crucial ingredient enters into the QM picture and it is the measurement process.
For a system to exhibit the interference effects resulting from QM state superpositions
it must not interact with the environment. These interactions are like independent mea-
surements of the system and they destroy its coherence (e.g. the two-state superposition)
by implicating (entangling them with) many external uncontrolled states. Now it is very
easy for a macroscopic system like a cat to interact with the world outside the box (for
example through the radiation it emits or adsorbs). Hence quantum experiments with
large objects are notoriously difficult to perform. So far the largest molecule for which
quantum interference effects have been demonstrated is the buckyball: C60 (see below).
Since the chiral states are given by:
24 QUANTUM MECHANICS
√
|1 > = ( |I > + |II >)/ 2
√
|2 > = (−|I > +|II >)/ 2 (2.17)
if the molecule has left-handed chirality to begin with: |Ψ(0) >= |1 >, it will evolve as:
0 0
e−iE I t/~ |I > + e−iE II t/~ |II >
|Ψ(t) >= √
2
The probability of finding the system with a left-handed chirality (state |1 >) after a
time t is: 0 0
|e−iE I t/~ + e−iE II t/~ |2
P1 (t) = | < 1|Ψ(t) > |2 = = cos2 (At/~)
4
and the probability of finding the system with right-handed chirality is P2 (t) = sin2 (At/~).
When a given molecule is measured its chirality is well defined (either left or right), but
measurements over many molecules yield the oscillating probability distribution just
computed. Since cos2 (At/~) = (1 + cos 2At/~)/2 the oscillation frequency is related to
the difference between the energy levels of the eigenstates ω0 = 2A/~. For NH3 that
frequency ν0 = ω0 /2π = 24 Ghz is in the microwave range. For NHDT it is slighly
lower due to the higher mass of Deuterium and Tritium.
The essence of Bell’s inequalities may be grasped from this simple example. Imag-
ine that a NHDT molecule prepared in a definite chiral state (|1 > or |2 >) is observed
a time δt later so that the probability of finding it in the same state is 99%. If it is
measured again a time δt later it will be observed in the same state as previously with
probability 99%. One may now ask: what is the probability of observing the system
in its initial state if we look at it a time not δt but 2δt later? If as Einstein believed
the system is at δt in a definite state that is only once in a hundred times different
from the initial state, then at 2δt the state of the system would be at worst twice in
a hundred times different from the initial state, namely the probability of observing
the system in its initial state would be at worst 98%. However the QM prediction is:
P(2δt) = cos2 (2Aδt/~) = 1 − 4(Aδt/~)2 = 0.96 (since we assumed that P(δt) = 0.99,
i.e. Aδt/~ = 0.1). The QM mechanical prediction violates the lower bound (the Bell
inequality) set by ”realistic” theories which assume that the system is in a definite state
which we have simply no way of determining, not a ”meaningless” superposition of
left and right-handed molecules. As mentioned earlier the experimental results (mea-
sured not on chiral amonia molecules but some other two-state system) vindicate the
QM prediction and rule out the ”realistic” theories.
electric dipole moment ~µ, as shown in Fig.2.6. In presence of an electric field E~ the en-
~ (Eq.??). If the electric field is along the x-axis in Fig.2.6,
ergy of a dipole is W = −~µ · E,
then we expect state |1 > to have higher energy than state |2 >. The Hamiltonian of the
molecule in an external electric field is thus:
E + W −A
!
H= 0
−A E0 − W
Notice that in the eigenbasis representation (where the unperturbed Hamiltonian H0 is
diagonal), the perturbed Hamiltonian can be written as:
E0 + A 0
! !
0 W
H 0 = ΛT HΛ = H0D + δH = + (2.18)
0 E0 − A W 0
√ √
The eigenvalues of H (and H 0 ) are: E I,II = E0 ± A2 + W 2 . Defining tan θ ≡ ( A2 + W 2 −
W)/A the eigenvectors of H are:
cos θ sin θ
! !
|I >= |II >=
− sin θ cos θ
When W = 0 one recovers the previous result. When W A: |I >' |1 > and |II >'
|2 >, in which case the enantiomers are also eigenstates. In practice however W =
µE A and the energies vary as: E I,II = E I,II0
± µ2 E 2 /2A. State |I > (with its dipole
essentially opposite to the electric field) has higher energy than state |II >. Notice that
we can write the energies E I,II in the following form (we will see later that this is a
general result when the diagonal Hamiltonian is perturbed by an amount δH)
δH12 δH21
E I = E I0 + (2.19)
E I0 − E II
0
δH21 δH12
E II = E II
0
+ 0 (2.20)
E II − E I0
These results suggest a way to separate the eigenstates by passing a beam of amonia
molecules through a strong electric field gradient. This field gradient generates a force
on the molecules:
~ I,II = ∓ µ ∇E
2
F~ I,II = −∇E ~ 2
2A
which separates them: state |I > is deflected to regions of small electric fields, while
state |II > is deflected to regions of high electric fields. Thus can a sub-population
inversion be generated where high energy amonia molecules are separated from lower
energy ones. This high energy sub-population can then be used to amplify microwave
radiaton by stimulated emission. The resulting device, known as a maser, was the first
implementation of a stimulated radiation amplification device and served as the first
atomic clock.
26 QUANTUM MECHANICS
F. 2.8. Principle of operation of a maser. An amonia beam (here the chiral molecule
NHDT) is sent trough a slit into a beam splitter that consists of a strong inhomoge-
nous electric field. At high field one can separate the different enantiomers which
are eigenstates of the energy. The high energy eigenstate (|I >) is sent into a cavity
where it goes into the low energy state |II > by emitting stimulated radiation at the
resonant frequency ω0 = (E I − E II )/~
which solution is αI (t) = cos Ω(t − t0 ) and αII = sin Ω(t − t0 ). The probability of being in
state |I > (α2I ) or II > (α2II ) oscillates with frequency 2Ω: the molecule go periodically
from stimulated emission in state |I > to adsorption in state II >. These oscillations
are different from the oscillations between the enantiomers |1 > and |2 > observed at
frequency ω0 in absence of electric field. This oscillation in the probability of observing
a specific enantiomer is not associated to emission of any radiation, it results from the
fact that the enantiomers are not eigenstates of the Hamiltonian: in absence of a time
varying electric field, if the molecule is in eigenstates |I > or |II > it remains there.
If the frequency of the electric field is slightly off resonance ω − ω0 ' 0 and if the
molecule remains in the cavity for a short time t 1/Ω we may assume that αI ' 1
and integrate the equation for αII to yield:
ei(ω−ω0 )t − 1
αII (t) = iΩ
i(ω − ω0 )
The probability of transition from state |I > to state |II > is then:
sin2 (ω − ω0 )t/2
PI→II (t) = |αII |2 = (Ωt)2
[(ω − ω0 )t/2]2
The function sinc x ≡ sin x/x decays rapidly for values of |x| > π. Hence the transition
rate is significant only for frequencies which are very close to resonance: |ω − ω0 | <
2π/t. If the molecule remains in the cavity for 1 sec, the relative possible detuning :
|ν/ν0 − 1| = 1/ν0 t ∼ 4 10−11 . Only frequencies within that very narrow range can be
amplified by stimulated emission. This allows for very high Q resonators, Eq.??, i.e.
very precise frequency generators and clocks. Because of the sharpness of the function
sinc2 (ω − ω0 )t/2 one often rewrites the previous equation using the limit
2π
lim sinc2 (ω − ω0 )t/2 = δ(ω − ω0 )
t→0 t
to obtain the transition rate from state |I > to |II >:
2π|δH21 |2
BII,I = δ(E I − E II − ~ω) = BI,II
~
which was the intuitive assumption Einstein made: the rate of stimulated emission BI,II
is equal to the rate of adsorption BII,I . Since the energies of the excited states are never
28 QUANTUM MECHANICS
perfectly sharp, due to the Heisenberg uncertainty principle that we shall see below and
due to thermal motion that leads to Doppler broadening of the emission lines (see sec-
tion??), the δ-function is replaced by the densityRof states with the appropriate energy:
ρ(E) (with E = E II + ~ω) and the normalisation ρ(E)dE = 1).
The amonia maser was the first atomic (or molecular) clock. The present genera-
tion of atomic clocks use a microwave transition in Cesium (Cs) as the reference fre-
quency for the clock. The atoms are cooled to very low temperatures (µ◦ K) to reduce
the Doppler broadening of their emission lines and keep them for as long as possible
in the cavity, usually a Penning trap (see ????). As a result the record for the frequency
precision of atomic clock is: |ν/ν0 − 1| ∼ 10−16 .
E0 −A 0 . . . −A
−A E −A . . . 0
0
H = . ..
(2.25)
.. .
−A . . . 0 −A E0
The eigenstates of that system obey: H|Ψ >= E|Ψ >, with |Ψ >= n Cn |n > From
P
which we derive the equations:
E − E0
C1 + C2 + Cn = 0
A
E − E0
C1 + C2 + C3 = 0
A
..
.
E − E0
C1 + Cn−1 + Cn = 0
A
Looking for a solution: Clm = exp i(2πlm/n) where l = 1, 2, ...., n we get:
El − E0
= −(ei2πl/n + e−i2πl/n )
A
Thus the eigen-energies of the system are:
El = E0 − 2A cos 2πl/n (2.26)
For benzene (n = 6) we have: E6 = E0 − 2A; E1,5 = E0 − A; E3 = E0 + 2A and E2,4 =
E0 + A. Energies E1,5,6 which are smaller that E0 are associated to so-called bonding
SIMPLE QM SYSTEMS 29
F. 2.9. Band-gap theory of material. (a) If the gap between the valence and conduction
band is large (a few electron-Volts) the material is an insulator. (b) Variation of the
band-gap energy with wave-vector k. Top curve: energy of electrons Ee ; bottom
curve: energy of holes Eh (increases towards the bottom). (c) A semi-conductor
which due to thermal excitation or illumination has some electrons in the conduction
band and some holes in the valence band. (d) a conductor is a material for which
the valence and conduction band overlap or equivalently for which an energy band
is not filled.
orbitals or wave-functions, whereas energies E2,3,4 > E0 are associated to anti-bonding
orbitals, on which we shall have more to say later. Notice that the eigen-state associated
√
to the maximally bonding orbital (l = 6) is fully symmetric: |Ψ6 >= (1, 1, 1, 1, 1, 1)/ 6,
while that associated to the maximally anti-bonding orbital (l = 3)√is antisymmetric to
the permutation of nearest neighbors: |Ψ3 >= (1, −1, 1, −1, 1, −1)/ 6.
The energy of the electron is bounded: E0 − 2A < E(k) < E0 + 2A. If each atom
contributes two electrons, these 2n electrons will occuy all the n-energy states (we shall
see later that each state can accomodate 2 electrons) and electron hoping in this energy-
band will be impossible. If however the on-site energy E0 can possess discrete values
(El as it does indeed, for example in Bohr’s model), the coupling of the n−atoms will
generate energy bands around each energy value El into which electron may hop. This
forms the basis of the band-theory of conduction in materials, see Fig.2.9: a material
will conduct if there are empty states into which electrons can hop. If the low energy
30 QUANTUM MECHANICS
F. 2.10. A p-type semiconductor consists of a material (usually Silicon, Si) doped
with an element (such as Aluminium) which having less electrons in its outer shell
than Si tend to trap electrons from the lattice, leaving a electron vacancy instead:
a hole. This depletes the valence bands of electrons allowing conduction through
motion of holes. A n-type semiconductor consists of a material doped with an elec-
tron donor, an element (such as Phosphate) which has more electrons in its outer
shell than Si. This injects electrons into the conduction band allowing the material
to conduct electricity. A pn-junction is formed when p-type and n-type semiconduc-
tors are brought in contact. Such a junction can be used as a Light Emitting Diode
(LED) when electron from the n-side of the junction recombine with holes from the
p-side. The wavelength of emitted light is determined by the energy-gap between
the conduction and valence and bands.
(valence) band is filled with electrons and the next (conduction) band is empty but
many electron-volts (eV) above it, then the electrons have no states in which to go and
the material is an insulator. If the conduction band overlaps with the valence band then
the electrons have empty states to hop to and current can flow in the material. The
interesting and technologically important case is the situation where the band-gap Eg
between the conduction and valence bands is small: Eg . 1eV (the gap for Silicon
(Si) is: Eg = 1.1eV; for Germanium (Ge): Eg = 0.72eV). In that case electrons can be
transfered from the valence to the conduction band by thermal agitation or via the photo-
electric effect resulting in a material that can behave either as a metal or an insulator
depending on the external conditions (temperature, voltage, illumination wavelength
and intensity, etc.).
In particular the introduction of atomic impurities (doping) that donate electrons to
(or accept electrons from) a semiconductor lattice creates a situation where few elec-
trons occupy an almost empty conduction band (or few holes (electron vacancies) oc-
cupy an almost full valence band). As we shall see later the electrons in an atom oc-
cupy certain orbitals or shells around the nucleus. Atoms (such as Phosphate or Ar-
senic) that have more electrons in their outer shell than the bulk semiconductor (the
so-called majority carrier, usually Silicon) will usually donate an electron to the lat-
tice, whereas atoms that have less electrons in their outer shell (such as Boron or Alu-
minium) will accept an electron from the lattice. The doping creates so called n- and
MOMENTUM AND SPACE OPERATORS 31
Doped semiconductors are the basic ingredients of all the semi-conductor industry
(transistors, diodes, integrated circuits, etc.). For example the coupling of p-type and
n-type semiconductors, generate a pn-junction which acts like a diode (current flows in
only one direction). It can also be used as a powerful and efficient light source. Electrons
in the n-type part of the junction can recombine with holes in the p-type (i.e. transit to
the valence band) with emission of light (just as in the atomic or molecular transitions
discussed earlier in the context of stimulated emission and the laser). The advantage
of these Light Emitting Diodes (LED) is that by appropriate tuning of the energy gap
(appropriate choice of the semi-conducting material) one can tune the wavelength at
which the LED will emit light. For example in the red and infrared part of the spectrum
Galium-Arsenide (GaAs) is the material of choice for LEDs. The intensity of light is
controlled by the current flowing through the junction. These LED are used in all kind
of electronic displays, in new high efficiency spot-lamps and traffic lights, in the remote
control of various electronic device, in the laser diode of DVD players, etc.
Where Ψ(x) is the probability amplitude of finding the particle at position |x >, so that:
Of course the probability of finding the particle somewhere is one, so that the wave-
function Ψ(x) is normalized:
Z
dxΨ∗ (x)Ψ(x) = 1 (2.29)
Z Z
1 1
Ψ(x) = √ dkΨ(k)eikx = √ d pΨ(p)eipx/~ (2.31)
2π 2π~
where we used de Broglie’s relations: p = ~k. Conversely:
Z
1
Ψ(p) = √ dxΨ(x)e−ipx/~ (2.32)
2π~
Ψ(p) is the wavefunction in the momentum (or Fourier) space: |Ψ >= p Ψ(p)|p >. For
P
the example chosen above the momentum wavefunction is:
e−ipx0 /~
Z ∞
dxe−(x−x0 ) /4σ e−ip(x−x0 )/~
2 2
Ψ(p) = √
2π~(2πσ ) 2 1/4 −∞
−ipx0 /~ −p2 σ2 /~2 Z ∞
e e
dxe−(x−x0 +2ipσ/~) /4σ
2 2
= √
2π~(2πσ2 )1/4 −∞
√
2σ/~ −ipx0 /~ −p2 σ2 /~2
= e e
(2π)1/4
Being the Fourier transform of Ψ(x), Ψ(p) satisfies the normalization condition:
MOMENTUM AND SPACE OPERATORS 33
Ψ∗ (p0 )Ψ(p)
Z Z Z
0
1= dxΨ∗ (x)Ψ(x) = d pd p0 dxei(p−p )x/~
2π~
Z Z
= d pΨ (p)Ψ(p) =
∗
d pP(p) (2.33)
Eq.2.33 is known in the theory of Fourier transforms as Parseval’s theorem. For a Gaus-
sian wavefunction Ψ(x) (see abovepexample) P(p) corresponds to a Gaussian centered
on p = 0 with standard deviation < (p− < p >)2 > = ~/2σ. The mean value of the
momentum satisfies:
Z Z
< p >= d pΨ∗ (p)pΨ(p) = d p0 d pΨ∗ (p0 )δ(p0 − p)pΨ(p)
Using the identity Eq.2.34 and Eq.2.31 allow us to express the momentum operator in
real space as:
Z
1 0
<p>= dxd p0 d pΨ∗ (p0 )ei(p−p )x/~ pΨ(p)
2π~
~ ∂
Z Z Z
1 0
= dx d p0 Ψ∗ (p0 )e−ip x/~ d p Ψ(p)eipx/~
2π~ i ∂x
~ ∂
Z Z
= ∗
dxΨ (x) Ψ(x) ≡ dxΨ∗ (x) p̂Ψ(x)
i ∂x
where we identify the momentum operator in real space as:
~ ∂
p̂ = ≡ −i~∂ x (2.35)
i ∂x
Similarly by writing the mean position < x > in momentum space we come to identify
the position operator in momentum space as:
∂
x̂ = i~ ≡ i~∂ p (2.36)
∂p
Notice that momentum and space-operators do not commute. In real space:
Z Z
~
< x|[x, p]|x >= dxΨ∗ (x)(x p̂ − p̂x)Ψ(x) = dxΨ∗ (x)[x∂ x Ψ − ∂ x (xΨ)] = i~
i
We would have obtainedR the same result by computing the commutator in momentum
space: < p|[x, p]|p >= d pΨ∗ (p)( x̂p − p x̂)Ψ(p) = i~. Since two observable cannot
share the same eigenstates if they do not commute, the position and momentum of a
particle cannot be simultaneously determined with absolute precision. The same result
holds also for the commutator of time and energy:
Z
< x|[H, t]|x >=< x|Ht − tH|x >= dxΨ∗ (x)(i~∂t t − ti~∂t )Ψ(x) = i~
34 QUANTUM MECHANICS
0 ≤ < φ|φ > = < ψ|(xo − iλpo )(xo + iλpo )|ψ >
= < ψ|xo2 + iλ[xo , po ] + λ2 p2o |ψ >
= < ψ|xo2 |ψ > −~λ+ < ψ|p2o |ψ > λ2 = P2 (λ)
For the quadratic polynomial P2 (λ) to be non-negative for any real λ, its determinant
has to satisfy:
~2 − 4 < ψ|xo2 |ψ >< ψ|p2o )|ψ >≤ 0
~2
< ∆x2 >< ∆p2 > ≥ (2.37)
4
~2
< ∆E 2 >< ∆t2 > ≥ (2.38)
4
~ · J~ = 0 ~ ~ Ψ∗ v̂Ψ + c.c.
∂t P + ∇ with J~ = Ψ∗ ∇Ψ + c.c. = (2.41)
2im 2
where c.c stands for the complex conjugate and v̂ = ~∇/im ~ is the velocity operator.
Eq.2.41 is a very important self-consistency check of Quantum Mechanics, since for
P(x) to be interpreted as a probability distribution it must satisfy a conservation law.
This equation expresses the intuitive expectation that the change in the probability of
finding a particle at a given position is equal to the particle flux gradient.
F. 2.11. The double-slit or Young’s experiment. (a) a wave passing through two slits in
a screen generates two wave-sources which interference creates on a far-away screen
a pattern of interference consisting of alternating minima and maxima of intensity.
(b) a particle in state |O > impinging on a double slit generates two states |I > and
|II > corresponding to its passage through slit 1 or 2. The phase of these states
evolves as exp ikl. If their coherence is maintained they can interfere on a screen a
large distance z from the slits, generating an oscillating pattern related to their phase
difference: φint = k(l2 − l1 ) = kd sin θ. (c) Observation of the interference pattern of
electron passing through a double slit and impinging on a camera. Each electron is
observed as a particle (white dot) with a well defined position on the camera. The
QM interference pattern is only visible when a sufficiently large number of particles
has been observed (A.Tonomura, Proc.Natl.Acad.Sci. 102, 14952 (2005).
One of the most striking confirmations of the QM mechanics picture is the obser-
vation of a diffraction pattern like the one seen with electro-magnetic radiation when
a free particle is passed through one or a few slits (see ??? and Fig.2.11(a)). Let the
particle be in an eigenstate
as it impinges on a screen that is absoring except for two apertures of size a a distance
d apart. In the far-field, i.e. at distances z d2 /λ the wave amplitude is given by
Huygens’s principle, Eq.??:
eik(z+(x +y )/2z
2 2 Z
dx0 dy0 e−i(kx x +ky y )
0 0
Ψdi f f (x, y, z) = (2.43)
iλz
Where k x = kx/z and ky = ky/z. Thus the probability of detecting a particle on a screen
a distance z from the slits is:
4a2
|Ψdi f f |2 = sinc2 k x a cos2 k x d/2 (2.44)
(λz)2
where sinc x ≡ sin x/x. If the distance between the diffraction slits is much larger than
their width (d a), the probability oscillates with a period: δx = λz/d. While each
SCHROEDINGER’S EQUATION 37
particle is observed as such, i.e. localized at a given position, the overall probability
distribution of the particles varies in space just as the diffraction pattern of EM radiation
does.
There is an other way to derive that result, see Fig.2.11(b). The wave-function of the
particle on the screen can be written as: |Ψ >= |I > +|II > where state |I >∼ eikl1 |O >
corresponds to the particle passing through the first slit and state |II >∼ eikl2 |O > to the
particle passing through the second slit. If the slits are assumed to be thin, i.e. a d,
then
|Ψdi f f |2 = < Ψ|Ψ >∼ |1 + eik(l2 −l1 ) |2 < O|O >= 4 cos2 kd sin θ/2
= 4 cos2 k x d/2 ≡ 4 cos2 (φint /2)
since l2 − l1 ' d sin θ ' xd/z. Notice that the interference pattern is observed only if the
phase-coherence between states |I > and |II > is maintained. For example if one wanted
to see through which slit the particle has passed, one would have to use radiation with
wavelength λo . d. Such radiation would impart on the detected particle a momentum
uncertainty δpo ∼ h/λo . In the far-field d2 /λz 1 the observation imparts on the
observed state a phase uncertainty:
which is enough to destroy the interference pattern. This is the essence of Heisenberg’s
principle: if the particle interacts with radiation of small enough wavelength as required
to determine its position the perturbation to its momentum will be so large as to destroy
the coherence of the states. Trying to determine through which slit the particle has
passed, namely to localize its position to better than the distance between the slits d,
imparts on the particle a momentum uncertainty large enough to destroy the interference
pattern, replacing it with an image of the two slits.
F. 2.12. The double-slit or Young’s experiment performed with the C60 molecule (Na-
ture 401, 680 (1999)). (a) Scanning tunneling microscope (STM) images of a C60
cluster and the reconstructed theoretical image of the cluster. (b) Schematic drawing
of the double slit experiment with C60 and the expected pattern, which is a cosine
wave modulated by the one-slit diffraction pattern (sinc2 k x a). (c) Upper plot: results
of the diffraction of the molecule from the slits (the continuous line is a best fit to
the theoretical prediction). Notice that the small side peaks are observed at a dis-
tance δx = λz/d ∼ 30µm from the central peak as expected for the diffraction from
two slits (see text). Bottom plot: the results when no slits are present and hence no
diffraction is expected (control experiment).
maintained with molecules at such high temperatures. The reason for that coherence is
that the particle is emitting black-body radiation at a wavelength of a few µm which is
much larger than the distance between the slits d ∼ 0.1µm. Hence the uncertainty in the
molecule’s momentum imparted by its black-body radiation is not enough to destroy
the coherence of the wave-function passing through contiguous slits.
In the forbidden region (i.e. within the wall: 0 < x < d) Schroedinger’s equation,
Eq.2.40
~2
− ∇2 Ψ + VΨ = EΨ
2m
has solutions of the form:
Ψo (x) = De−κx + Eeκx
√
with κ = 2m(V − E)/~. At the interface with the wall (at x = 0 and x = d) the
continuity of the wavefunction and its first derivative require that:
A+B = D+E
ik(A − B) = κ(−D + E)
Ceikd = De−κd + Eeκd
ikCeikd = κ(−De−κd + Eeκd )
C 4k2 κ2
T = | |2 =
A 4k2 κ2 + (k2 + κ2 ) sinh2 κd
4E(V − E) 16E −d/λt
= → e when : E V and κd 1
4E(V − E) + V sinh κd
2 2 V
Where λt = 1/2κ is the typical tunneling length. For an energy barrier V = 1eV: λt '
1Å which is the typical size of an atom. The transmission probability thus decreases
exponentially with the size d of the gap which can be but a few Å wide.
This sensitivity of QM tunneling to atomic size dimension has led to the develop-
ment in 1981 of the Scanning Tunneling Microscope (STM) by Gerd Binning and Hein-
rich Rohrer. They used it to image surfaces with atomic resolution and were awarded
for it the Nobel prize in Physics in 1986. In a STM a conducting tip is scanned above
a conducting surface, see Fig.2.13(b). The electrons tunnelling between the tip and the
surface (across an insulating gap, usually vacuum) generate a current which amplitude
is exponentially sensitive to the size of the gap and the voltage across it. A piezo-electric
tube displaces the tip above the surface while maintaining a constant current, namely a
fixed distance between the tip and the surface via an appropriate feedback loop. Mea-
suring the amplitude of the feedback signal while scanning the tip generates an image of
the surface with atomic resolution, Fig.2.13(c). This invention revolutionized the study
of matter at the nanoscale. It also led to the development of many other scanning probe
microscopes, such as the Atomic Force Microscope (AFM) which uses the deflection
of a small cantilever, like the needle in a gramophone, to map a surface with atomic
resolution.
40 QUANTUM MECHANICS
F. 2.13. (a) An electron wave of energy E is incident on a barrier of energy V. Some
of the wave is reflected and some tunnels through the barrier to be transmitted.
(b) The principle of the Scanning Tunneling Microscope (STM). A conducting tip
mounted on a piezo-electric drive is scanned across a surface. The current tunneling
between the surface and the tip is kept constant via an appropriate feedback loop that
maintains a constant distance between tip and surface. The feedback signal is used
to generate an image of the surface with atomic resolution. (c) Image of the surface
of a gold crystal taken in vacuum at 77◦ K. To minimize their surface energy the gold
atoms deviate from the bulk crystal structure and arrange in columns several atoms
wide with regularly-spaced pits between them.
The STM also made possible the study of QM problems which for decades were
assumed to be thought experiments, such as the problem of finding the eigen-energies
of a particle confined in a 2D box. With the help of an STM such a situation could be
constructed and studied: consider for example the case of a free particle (an electron
on the surface of a conductor (Cu) with effective mass m∗ = 0.38me ) confined in a two
dimensional ring of radius a = 71.3Å formed by 48 atoms of iron (Fe) deposited and
manipulated with an STM to form a corral, Fig.2.14. The Schroedinger equation for
such a particle is:
~2
− ∗ ∇2 Ψ = EΨ
2m
for r < a and Ψ = 0 for r > a. This is a typical Helmholtz equation (see Ap-
pendix) which solutions are: |n, l >≡ Ψn,l (r, φ) = Jl (κn,l r)eilφ where the eigen-energies
En,l = ~2 κn,l
2
/2m∗ are determined by the boundary condition Jl (κn,l a) = 0. Fig.2.14
presents the results from the group of Don Eigler at IBM who observed with an STM
the wavefunction of an electron trapped in such a corral. The measured tunneling cur-
rent is proportional to the probability of finding the electron under the scannig tip, which
THE CORRESPONDANCE PRINCIPLE 41
F. 2.14. Electrons on the surface of copper (Cu) with effective mass m = 0.38me
are confined in a corral of radius a = 71.3Å formed by 48 atoms of iron (Fe), see
Crommie et al., Science 262, 218 (1993). The probability of finding an electron at a
given place within the corral is proportional to the intensity of the current tunneling
into the scanning conducting tip of an STM. The observations are remarquably fit
by a linear superposition of just three eigen-functions, solutions of Schroedinger’s
equation for this problem.
is remarquably fit by a linear combination of just three eigenstates: |5, 0 >, |4, 2 > and
|2, 7 > with similar energies (since: κ5,0 a = 14.931, κ4,2 a = 14.796 and κ2,7 a = 14.821).
In this corral the surface electrons with the highest energy are thus occupying the top of
the conduction band from which they hop into the tip of the STM.
which is indeed the classical result ~p = m~v. Similarly the evolution of the velocity
operator yields:
d < [ x̂, Ĥ] > < [ x̂, ( p̂2 − (q/c)(Â p̂ + p̂Â))] >
< x̂ > = =
dt i~ 2i~m
< [ x̂, p̂2x ] > −2(q/c)Â x [ x̂, p̂ x ] >
=
2i~m
< p x − (q/c)A x >
=
m
~ f )2
( p̂ − (q/c)Â − (q/c)∇
Ĥ 0 =
2m
However this transformation can be compensated by a similar gauge transformation on
the wavefunction:
Ψ0 (x) = eiq f /~c Ψ(x)
In that case:
THE CORRESPONDANCE PRINCIPLE 43
In general the extra phase q f /~c has no effect on the probability of detecting a parti-
cle at a given position, since it depends on the absolute value of Ψ(x). There is however
a situation first pointed out by Aharonov and Bohm in 1959 where this gauge transfor-
mation leads to detectable effects. This happens when the probability of detecting an
electron in presence of a magnetic field results from the interference between different
paths the electron can follow, as in the diffraction experiment shown in Fig.2.11 and
Fig.2.15. Following our earlier derivation, the wave-function of the particle on a screen
far away from the diffraction slits is:
44 QUANTUM MECHANICS
~ r ~ r
|Ψ > = |I > +|II >= eikl1 +i(q/~c) |O > +eikl2 +(q/~c)
R R
1
A·d~ 2
A·d~
|O >
~ r
H
= (1 + e ik(l2 −l1 )+i(q/~c) A·d~
)|O >
= (1 + e ik(l2 −l1 )+iδφ
)|O >
where the phase difference δφ is related to the magnetic flux Φ enclosed by the interfer-
ing paths:
I I I
~ ~ ~ ~
δφ = (q/~c) A · d~r = (q/~c) ∇ × A · dS = (q/~c) B ~ · dS~ = qΦ/~c
Hence the enclosed magnetic flux can change the pattern of interference of the elec-
tron wavefunction, even if the electron does not (and cannot) pass through the region
containing the magnetic field and no force is exerted on it! As shown in Fig.2.15, this
effect has been clearly evidenced using superconducting materials to prevent leakage
of the magnetic field. Notice that the interference pattern is periodic in Φ with a pe-
riod ∆Φ = hc/q a property which is used to measure the magnetic field in extremely
sensitive Superconducting Quantum Interference Devices (SQUID).
∂Ψ √ 2 2 2
i~ = −~ c ∇ + m2 c4 Ψ
∂t
led to insurmountable problems related to the interpretation of the square-root of the
momentum operator. Similarly writing H 2 = p2 c2 + m2 c4 to derive the so-called Klein-
Gordon equation:
∂2 Ψ
= [∇2 − (mc/~)2 ]Ψ (2.47)
∂(ct)2
yields an equation which is second order in time (Schroedinger’s equation is first order)
and does not allow for the interpretation of |Ψ|2 as a probability density. Dirac searched
for a relativistic formulation that like Eq.2.16 would be first order in time, yet would
treat time and space in a relativistic invariant way. He noticed that he could obtain
DIRAC’S EQUATION: ANTIPARTICLES AND SPIN 45
∂2 X X
[∇2 − ]|Ψ(x, t) >= ( Ak ∂ xk + i(β/c)∂t )( Ak ∂ xk + i(β/c)∂t )|Ψ(x, t) >
∂(ct)2
Where Ak , β are hermitian matrices that satisfy the following relations: A2k = β2 = 1 and
Ak A j + A j Ak = Ak β + βAk = 0 (for k , j). To satisfy these 10 equations the matrices
have to be at least 4 × 4 matrices and the eigenvectors are 4-vectors which satisfy:
X
( Ak ∂ xk + i(β/c)∂t )|Ψ >= mc/~|Ψ >
0 σk
! !
I 0
αk = β= (2.49)
σk 0 0 −I
which expresses a conservation law for the probability density P(x, t) =< Ψ(x, t)|Ψ(x, t) >
with current density Jk = c < Ψ|αk |Ψ >:
∂P ~ ~
+∇·J =0
∂t
46 QUANTUM MECHANICS
Let us now investigate Eq.2.48. Let us first consider a free electron with zero mo-
mentum. The equation is then:
which solutions are |Ψ0 >1,2 = e−i(mc /~)t (φ̃0 , 0, 0) and |Ψ0 >3,4 = ei(mc /~)t (0, 0, χ̃0 ) where
2 2
φ̃0 and χ̃0 are 2D vectors. The first solution describes an electron with positive energy
Ee = mc2 and the second a hole with energy Eh = −mc2 on which we will have more to
say shortly.
Let us look for a solution in terms of the two-component vector: |Ψ >= (φ̃, χ̃). Dirac’s
equation can then be recast as:
φ̃ χ̃ φ̃ φ̃
! ! ! !
= c k σk πk + qΦ + mc2
P
i~∂t (2.52)
χ̃ φ̃ χ̃ −χ̃
To obtain the low energy limit of Dirac’s equation we look for a solution which is a
perturbation of the previous solution for positive energy Ee = mc2 at zero momentum:
Where φ and χ are slowly time-varying fields (i.e. slower than ω0 = mc2 /~), solutions
of the coupled equations:
φ χ φ
! ! ! !
0
= c k σk πk + qΦ − 2mc2
P
i~∂t (2.54)
χ φ χ χ
In the low energy limit (when mc2 is larger than any other energy) the field χ is slaved
to φ (i.e. all terms in χ are negligible with respect to the 2mc2 χ term) and thus:
σk πk φ
P
χ= k
2mc
which yields the following equation for φ:
( σk πk )2
P
i~∂t φ = [ k + qΦ]φ
2m
Using the following property of Pauli matrices:
DIRAC’S EQUATION: ANTIPARTICLES AND SPIN 47
~ σ · B)
σ · A)(~
(~ ~ =A
~·B
~ + i~ ~×B
σ·A ~
one obtains:
σ · ~π)2 = π2 + i~
(~ σ · ~π × ~π
= π + i~
2
σ · (−i~∇ ~ − (q/c)A) ~ − (q/c)A)
~ × (−i~∇ ~ (2.55)
= π − (~q/c)~
2 ~ ×A
σ·∇ ~ = π2 − (~q/c)~ ~
σ·B
From which one obtains the low energy version of Dirac’s equation:
( p̂ − (q/c)Â)2 ~ + qΦ] φ
i~∂t φ = [ σ·B
− (~q/2mc)~ (2.56)
2m
which ressembles Schroedinger’s equation except for the additional term on the right
hand side which is the energy of a dipole m ~ = (~q/2mc)~ ~ Hence
σ in a magnetic field B.
Dirac’s equation implies that the electron possesses an intrinsic magnetic moment, a
fact that was known from the spectrum of atoms in a magnetic field (see below). Exem-
plifying yet again the ”unreasonable effectiveness of Mathematics” it is amazing that
this intrinsic properties of the electron is a mathematical consequence of the unification
of QM and relativity!
Moreover Dirac’s was able to relate this magnetic moment to the intrinsic angular
momentum of the particle. Consider the time evolution in abscence of magnetic field of
the angular momentum ~L = ~r × ~p. As we have seen the time evolution of an observable
obeys:
X
i~∂t < L x > = < [L x , H] >=< [ypz − zpy , (c αk pk + mc2 β)]
k
= c < αy [y, py ]pz − αz [z, pz ]py >= i~c < αy pz − αz py >, 0
Thus in Dirac’s equation < L x > is not a constant of motion, in contrast with the
Schroedinger’s equation for a free particle where it is. Now consider the evolution of σ̂ x
(the 4 × 4 matrix which diagonal elements are the Pauli σ x matrices):
X
i~∂t < σ̂ x > = < [σ̂ x , H] >=< [σ̂ x , (c αk pk + mc2 β)]
k
= c < [σ̂ x , αy ]py + [σ̂ x , αz ]pz >= 2ic < αz py − αy pz >
Where we used the following property of Pauli’s matrices: [σ x , σy ] = 2iσz , [σ x , σz ] =
−2iσy . Therefore L x + ~σ̂ x /2 commutes with the Hamiltonian, i.e. it is a constant of
the motion. Dirac interpreted this result to mean that the particle has a spin angular
momentum S~ = ~~ σ/2 which must be added to the orbital angular momentum ~L to get
the total angular momentum, J~ = ~L + S~ which is a constant of the motion.
According to Eq.2.56, the magnetic dipole moment of the electron is related to its
spin by:
m σ = (qg/2mc)S~
~ = (~q/2mc)~ (2.57)
Where g = 2 is known as the gyromagnetic ratio. This is in contrast with the mag-
~ = (q/2mc)~L (see Eq.??) for which
netic moment arising from the angular momentum m
48 QUANTUM MECHANICS
g = 1. The prediction of the gyromagnetic ratio of the electron was an other success
of Dirac’s equation. In fact the value of g has become the most stringent test of quan-
tum electro-dynamics (QED), the theory that generalized Dirac’s approach and unified
Electromagnetism and Quantum Mechanics. It is the most precisely known constant of
nature: its value has been tested to 12 decimal places g = 2.0023193043617(!!), making
QM and QED the most precisley tested theories ever proposed.
Let us now return to the hole solution with energy Eh = −mc2 . We have already seen
such solutions when studying the band theory of solids. In fact the original interpretation
of Dirac was very similar. He assumed that all negative energy levels were occupied by a
”sea” of electrons. Out of this sea, electrons could be excited to an energy level Ee = mc2
leaving behind a hole (or positron) of energy Eh = mc2 . This process, electron-positron
creation (and its reverse, annihilation) is routinely observed in particle accelerators once
an energy E > 2mc2 ∼ 1MeV is achieved. The dynamic behaviour of the positron is
similar to that of an electron with opposite charge. To derive the positron wave-equation
at low energies, we shall follow our previous study of the electron in a similar regime.
We look for a low energy solution:
φ̃ i(mc2 /~)t φ
! !
|Ψ >= =e (2.58)
χ̃ χ
Which leads to the following equation for the positron-wavefunction at low energies:
σk πk )2
P
(
i~∂t χ = [− k
+ qΦ]χ
2m
Since the Pauli matrices are hermitian, the equation for the complex conjugate of χ is:
σk (i~∂ xk − (q/c)Ak )2
P
( k
i~∂t χ = [
∗
− qΦ]χ∗ (2.59)
2m
( k σk (−i~∂ xk + (q/c)Ak )2
P
=[ − qΦ]χ∗ (2.60)
2m
This is the low energy limit of Dirac’s equation for a particle of mass m and charge −q.
As seen above in the band-gap theory of conduction in solids, the hole solution describes
the behaviour of a particle of the same mass as the electron and of opposite charge. This
prediction of Dirac was vindicated by the discovery of the positron three years later by
Carl Anderson, for which they both shared the 1933 Nobel prize in Physics.
To summarize, the unification in 1929 of relativity and QM by Dirac led to many
unexpected predictions of which we have seen three:
1) the existence of anti-particles (e.g. the positron) of mass identical to the particle
and with opposite charge. These are created when an energy 2mc2 is available to create
for example an electron-positron pair (raise the electron from the top of the ”sea” at
Eh = −mc2 to the electron rest energy Ee = mc2 ).
DIRAC’S EQUATION: ANTIPARTICLES AND SPIN 49
~2 2 ~2 1 ∂2 1 ∂ ∂ 1 ∂2
H=− ∇ =− { r+ 2 sin θ + } (2.61)
2m 2m r ∂r 2 r sin θ ∂θ ∂θ r2 sin θ ∂φ2
2
~2 ∂2 2 ∂ ~2 2
=− { 2 + }− L (2.62)
2m ∂r r ∂r 2mr2
The operator : L̂2 = −~2 L2 is known as the angular momentum operator, since its
R L̂ /2mr is the classical angular momentum kinetic
2 2
contribution to the Hamiltonian, i.e.
energy: E L = L2 /2I (whereI = d3 rρ(r)r2 is the moment of inertia). As shown in
the Appendix on the Helmholtz equation, the eigenfunctions of L2 are the spherical
harmonics Ylm [θ, φ) with eigen-value −l(l + 1), hence:
L̂2 |l, m > = ~2 l(l + 1)|l, m >
s
(2l + 1)(l − m)! m
with :|l, m > = Ylm [θ, φ) = Pl (cos θ)eimφ (2.63)
4π(l + m)!
The eigenfunctions of L̂2 are also eigenfunctions of L̂z with eigenvalue ~m:
L̂z |l, m >= ~m|l, m >
Notice that L̂z does not commute with L̂ x or L̂y . In fact these operators satisfy the fol-
lowing commutation relations:
[L̂ x , L̂y ] = i~L̂z
[L̂ x , L̂z ] = −i~L̂y
[L̂y , L̂z ] = i~L̂ x
or : [L̂i , L̂ j ] = i~i jk L̂k (2.67)
50 QUANTUM MECHANICS
where i, j, k stands for x, y or z and i jk = 1 for an even permutation of the indices and
−1 for an odd permutation. As we shall see below, it is usefull to define the raising and
lowering operators:
∂ ∂
!
L̂± = L̂ x ± L̂y = ~e ±iφ
± + i cot θ
∂θ ∂φ
Notice that L̂2 = L̂2x + L̂y2 + L̂z2 = L̂z2 + L̂+ L̂− − ~Lz = L̂z2 + L̂− L̂+ + ~Lz commutes with L̂z
but also with L̂ x , L̂y , L̂± .
[L̂2 , L̂ x ] = [L̂y2 , L̂ x ] + [L̂z2 , L̂ x ] = L̂y [L̂y , L̂ x ] + [L̂y , L̂ x ]L̂y + L̂z [L̂z , L̂ x ] + [L̂z , L̂ x ]L̂z
= −i~L̂y L̂z − i~L̂z L̂y + i~L̂z L̂y + i~L̂y L̂z = 0
These operators therefore do not mix eigenstates with different values of l but since they
do not commute with L̂z they do mix eigenstates with different values of m. Using their
commutation rules one can show that L̂± |l, m >∼ |l, m ± 1 >. Consider for example the
commutation relations for L̂+ :
−~L̂+ |l, m > = [L̂+ , L̂z ]|l, m >= (L̂+ L̂z − L̂z L̂+ )|l, m >
= ~mL̂+ |l, m > −L̂z L̂+ |l, m >
namely : L̂z (L̂+ |l, m >) = ~(m + 1)(L̂+ |l, m >)
Hence:
L̂± |l, m >= a±lm |l, m ± 1 >= ~ (l + 1) − m(m ± 1)|l, m ± 1 >
p
(2.68)
Where the coefficient a+lm is determined by the normalization condition:
|a+lm |2 = |a+lm |2 < l, m + 1|l, m + 1 >=< l, m|L̂+∗ L̂+ |l, m >=< l, m|L̂− L̂+ |l, m >
= < l, m|L̂2 − L̂z2 − ~Lz |l, m >= ~2 (l(l + 1) − m(m + 1))
Notice that the action of L+ on a state |l, m > is to generate the higher m-state
|l, m + 1 > whereas the action of L− on |l, m > generates the lower m-state l, m − 1 >,
which justifies their name as raising and lowering operators.
Since the spin is also an angular momentum operator the same commutation rela-
tions exist between Ŝ 2 , Ŝ x , Ŝ y , Ŝ z and Ŝ ± . For spin one-half particles, the eigenstates
DIRAC’S EQUATION: ANTIPARTICLES AND SPIN 51
|s, sz > of Ŝ 2 = ~2 σ2 /4 and Ŝ z = ~σz /2 with eigenvalues s(s + 1)~2 = 3~2 /4 and
~sz = (±1/2)~ are:
! !
1 0
|1/2, 1/2 >= |1/2, −1/2 >=
0 1
We have seen that one of the results of Dirac’s equation is that spin and angular mo-
mentum operators L̂z , Ŝ z do not commute with the Hamiltonian and are therefore not
good (i.e. conserved) quantum numbers. Rather the total angular momentum operator:
Jˆz = L̂z + Ŝ z with eigenvalue k = m + sz is conserved, together with Jˆ2 , L̂2 and Ŝ 2 . Thus
the eigenstate of the total angular momentum is: | j, l, s, k >. Since m = k ∓ 1/2 and the
eigenstates of the angular momentum are Ylm we can write:
! !
1 0
| j, l, s, k >= c1 |l, k−1/2 > |s, 1/2 > +c2 |l, k+1/2 > |s, −1/2 >= c1 Yl,k−1/2 + c2 Yl,k+1/2
0 1
3 L̂σ
Jˆ2 | j, l, s, k >= ~2 [l(l + 1) + + ]| j, l, s, k >= ~2 γ| j, l, s, k >
4 ~
Using the relation:
!
Lz L−
L̂σ = L̂ x σ x + L̂y σy + L̂z σz ==
L+ −Lz
and the previously derived equation for the raisng and lowering operators, Eq.2.68, one
obtains the following eigenvalue equation for γ:
√
l(l + 1) + 1/4 + k − γ l(l + 1) − (k − 1/2)(k + 1/2)
= 0
√
l(l + 1) − (k − 1/2)(k + 1/2) l(l + 1) + 1/4 − k − γ
which solution is γ = j( j+1) with j = l±1/2. Hence the eigenvalues of the total angular
momentum operator Jˆ2 are ~2 j( j + 1) with eigenfuctions:
√
√ l + k Yl,k−1/2
!
1
| j, l, s, k > = |l + 1/2, l, 1/2, k >= √
2l + 1 l − k + 1 Yl,k+1/2
√
k + 1 Yl,k−1/2
!
1 l−
| j, l, s, k > = |l − 1/2, l, 1/2, k >= √ √
2l + 1 − l + k Yl,k+1/2
52 QUANTUM MECHANICS
~2 2 Ze2
− ∇ Ψ(~x, t) − Ψ(~x, t) = En Ψ(~x, t) (2.69)
2me r
where the −Ze2 /r term stands for the Coulomb interaction between the orbiting electron
(of mass me ) and a nucleus containing Z protons (in Hydrogen Z = 1). In spherical
coordinate the differential operator can be written as:
∂2 2 ∂ 1 1 ∂ ∂ 1 ∂2
∇2 = + + [ (sin θ ) + ]
∂r2 r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2
As for the Helmholtz problem (see Appendix) we look for a eigen-function:
where the spherical harmonics Ylm (θ, φ) are eigen-functions of the angular operator (see
above):
1 ∂ ∂ 1 ∂2
L2 Ylm (θ, φ) = [ (sin θ ) + ]Ylm (θ, φ) = −l(l + 1)Ylm (θ, φ)
sin θ ∂θ ∂θ sin2 θ ∂φ2
The equation for the radial function Rnl (r) then becomes:
~ 2 ∂2 2 ∂ ~2 l(l + 1) Ze2
[− ( 2+ )+ − ]Rnl = En Rnl
2me ∂r r ∂r 2me r2 r
The first term on the left is the radial part of the kinetic energy, the second term is the
centrifugal potential (the angular part of the kinetic energy) and the third term is the
Coulomb repulsion. Writing Rnl (r) = unl (r)/r yields the following equation for u(r):
Defining a = 2Zme e2 /~2 ≡ 2/r0 and λ2n = −2me En /~2 one can recast the previous
equation as:
a l(l + 1)
u00nl + ( − )unl = λ2n unl
r r2
In the limit r → ∞, the terms in the bracket on the left hand side are negligible and
the solution in that limit is unl (r) ∼ exp(−λn r). Let us therefore look for a solution:
unl (r) = µnl (r)exp(−λn r). The equation that µnl (r) obeys is:
THE HYDROGEN ATOM AND ELECTRONIC ORBITALS 53
a l(l + 1)
µ00nl − 2λn µ0nl + ( − )µnl = 0
r r2
Notice that close to r = 0 the solution behaves as µnl (r) ∼ rl+1 . Let us therefore look
for a polynomial solution: µnl (r) = nj=1 c j r j . The coefficient of the term of order j − 1
P
reads:
j( j + 1)c j+1 − 2λn jc j + ac j − l(l + 1)c j+1 = 0
which yields:
2λn j − a
c j+1 = cj
j( j + 1) − l(l + 1)
To be defined for all values of j the series {c j } must start at j = l + 1 (the small r limit
of µnl (r)) and to be finite it must end at a value l < j = n for which: a = 2nλn , i.e. for a
value of the eigen-energy, En :
~2 λ2n ~2 1
En = − =−
2me 2me r02 n2
which is the result obtained by Bohr, see Eq.2.8. Notice that while the radial eigen-
functions depend on the two quantum numbers n, l, the eigen-energies depend only on
n. This is a peculiarity of central potentials (such as the Coulomb potential between
proton and electron). In non-hydrogen atoms that degeneracy is raised due to the extra
Coulomb repulsion between the electrons. It is customary to label the various orbitals
(the hydrogen atom’s eigensolutions) by their shell number n = 1, 2, 3, .... and their
main angular momentum number l, such that l = 0 is called the s-orbital; l = 1 the
p−orbital; l = 2 the d−orbital; l = 3 the f −orbital; l = 4 the g−orbital ... etc. (in
alphabetical order skipping j). With this nomenclature we can proceed to write down
the radial eigen-functions Rnl (r) = µnl (r) exp(−r/nr0 )/r for the first orbitals:
In abscence of other terms in the Hamiltonian, the orbitals of the electron in the
Hydrogen atom are degenerate, i.e. for different values of the spin and angular quantum
numbers (l, m) the energy of the electron is the same. Since there are 2 possible spin
states for every eigenfunction Ψnlm and 2l + 1 states with different values of m (and
same value of l: −l ≤ m ≤ l) and since 0 ≤ l ≤ n − 1, the degeneracy of a state
with shell number n is: 2n2 . As we shall see next this degeneracy is partially raised by
various relativistic effects (for example by the interaction between the electron spin and
the magnetic field the electron generates when orbiting the nucleus, so-called spin-orbit
coupling), by the action of external fields or by the presence of other electrons.
54 QUANTUM MECHANICS
moving at velocity −~v and is generating both electric and magnetic fields. If the electron
frame of reference was inertial (i.e. if the electron was moving in a straight line) then
the magnetic field experienced by the electron would be
~ = − ~p × ~r e = e ~L
~ = −~v × E/c
B
me c r3 me cr3
This magnetic field which is parallel to the angular momentum ~L = ~r × ~p, interacts with
the electron spin S~ = ~~
σ/2 to contribute an energy, see Eq.2.56:
δH so =
~e ~ = e S~ · B
~ ·B
σ ~
2me c me c
Since the electron frame is not inertial the final result differs by a factor 2 from this
estimate:
e2 ~ ~
δH so = S · L ≡ g so S~ · ~L
2m2e c2 r3
As was argued by Dirac (see above), Lz and S z are not eigenvalues of the relativistic
Hamiltonian, rather the projection of the total angular momentum Jz = Lz + S z is.
Rewriting 2S~ · ~L = J 2 − L2 − S 2 one can write the Spin-orbit contribution as:
e2
δH so = (J 2 − L2 − S 2 )
4m2e c2 r3
Its contribution is best estimated in the basis which commutes with Dirac’s Hamiltonian,
i.e. in terms of eigenstates | j, l, s, k > of J 2 , L2 , S 2 and Jz :
δE so =< j, l, s, k|δH so | j, l, s, k >
To compute how that spin-orbit coupling modifies the energy spectrum of the Hydrogen
atom computed above, first notice that it couples between eigenstates with the same
value of l but different values of j, i.e. j = l ± 1/2. Hence the term: J 2 − L2 − S 2
with eigenvalue: j( j + 1) − l(l + 1) − 3/4 can have two values: ~2 l (if j = l + 1/2) and
−~2 (l + 1) (if j = l − 1/2). The term in 1/r3 in δH so can be computed directly from the
radial solutions Rnl of the Hydrogen atom with the result:
e2 e2
gnl ≡< n, l| |n, l >=
4m2e c2 r3 2m2e c2 a30 n3 l(2l + 1)(l + 1)
THE HYDROGEN ATOM AND ELECTRONIC ORBITALS 55
Thus because of the relativistic coupling between the electron’s angular momentum and
its spin the energy levels of the Hydrogen atom with same values of n and l are split in
two:
e2 ~2
(
l
δE ±so =
2m2e c2 r3 n3 l(2l + 1)(l + 1) −l − 1
0
Notice that that the spin-orbit interaction is a very small (yet measurable) perturbation
to the electronic energies of the hydrogen atom:
|En | e2
δE so ∼ ∼ 7.4 10−4 eV |En |
me c2 r0
Where we used the fact that e2 /2r0 = |E1 | = 13.6 eV and me c2 = 0.5MeV.
Consider the Hamiltonian of a two particle system Ĥ(1, 2). Because of the iden-
tity of the particles the Hamiltonian is unchanged upon a permutation of the particles:
Ĥ(1, 2) = Ĥ(2, 1). Hence the permutation operator P̂ commutes with the Hamiltonian:
and is a constant of motion. Two successive permutations brings us back to the initial
state: P̂2 = 1 which implies that the eigenvalues of the permutation operator are ±1:
|2, 1 >= P|1, 2 >= ±|1, 2 >. These eigenvalues are constants of motion, namely the
wavefunction of a many particles system is either even or odd under permutation of its
(identical) particles. Like spin this is a QM property of the particle. Particles known
as fermions (electrons, protons, neutrons, etc.) are odd under permutations: |2, 1 >=
−|1, 2 >, while particles which are even under permutation |2, 1 >= |1, 2 > are known
as bosons (e.g. photons). In 1940 Wolfgang Pauli, requiring QM to be invariant under a
change of reference frames (relativistic invariance), related this permutation property to
the spin of the particle: particles with half integer spin are fermions while particles with
integer spin are bosons.
56 QUANTUM MECHANICS
If the particles can occupy states |ψ > and |φ >, then for two bosons the joint wave-
function |1, 2 > (symmetric under exchange of the particles) is:
|ψ(1) > |φ(2) > +|ψ(2) > |φ(1) >
|1, 2 >= √ = |2, 1 >
2
For two fermions the joint wavefunction is:
|ψ(1) > |φ(2) > −|ψ(2) > |φ(1) >
|1, 2 >= √
2
which is an eigenfunction of the permutation operator P with eigenvalue -1: |2, 1 >=
P|1, 2 >= −|1, 2 >. This wavefunction implies that in contrast to bosons, two fermions
cannot share the same eigenfunctions: |ψ >, |φ >. If their spatial wavefunction is iden-
tical then their spin-state must differ and if their spin-state is identical then their spatial
wavefunction must differ. This extremely important property of fermions is known as
Pauli’s exclusion principle. It implies that the lowest energy level of an electronic sys-
tem can be occupied by at most two electrons (with opposite spins). Contrast that with
the situation for bosons where the lowest energy state can be occupied by an arbitrary
number of particles (for example photons of same energy as in Plank’s black body radi-
ation).
F. 2.16. The orbital energies of many-electron atoms. The energy levels are ordered
along the abscissa according to the main shell number n, which is also indicative
of the size of the atom (the spread of the radial wavefunction increases roughly as
nr0 ). Notice that levels with different angular quantum number l (different colors)
have different energies, though they are still degenerate with respect to the azymutal
quantum number m: the number of circles indicate the level of degeneracy 2l + 1.
Notice that in abscence of an external field there is no preferred axis that would
break that azymutal symmetry. To minimize the energy electrons fill these levels
from the bottom up while satisfying Pauli’s principle: no more than two electrons
(with opposite spin) per energy level. The first level to be filled is 1s, then 2s, 2p,
etc... Notice that the more outer orbitals 4s having lower energy is filled before 3d;
5s before 4d and 6s before 4 f and 5d.
property of Lithium with one valance electron in the same s−state as the electron in
Hydrogen imply similar chemical properties, as indeed all the alkalines (the elements in
the first column of Mendeleev’s table, see Fig.2.17: Sodium (Na), Potassium (K), Ru-
bidium (Rb), Cesium (Cs), Francium (Fr)) which all have a single electron in an s−state.
In spectroscopic notation the state of the electron in the unfilled shell is: 2S +1 L J =2 S 1/2 ,
which is the same as Hydrogen. Since (as we shall see below) it is the electronic state in
the outer shell that determines the chemical characteristics of the element the chemical
properties of Lithium and hydrogen are similar.
Beryllium (Be) has four electrons, two occupying with opposite spin the lowest
orbital (1s)2 and two electrons occupying the next orbitals (2s) with opposite spin. Its
electron occupancy is thus: (1s)2 (2s)2 which is similar to Helium. Beryllium is however
more reactive than Helium since its 2p orbital has an energy only slightly higher than
58 QUANTUM MECHANICS
F. 2.17. The periodic-table of the elements. The periodic table devised by Mendeleev
and ordered according to increasing atomic number (number of electrons) and sim-
ilar chemical properties. In comparison the table is redrawn as deduced from the
filling up of the orbitals from the bottom up, taking into account Pauli’s exclusion
principle and ordering the columns according to the number of valence (outer shell)
electrons. The agreement between the two is one of the greatest success of QM.
2s which result in the electron easily hoping to the 2p orbital. Its outer shell electron oc-
cupancy is identical to that of Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium
(Ba) and Radium (Ra) which have similar chemical properties.
Boron (B) has 5 electrons, two in orbital 1s, two in orbital 2s and one in orbital 2p:
(1s)2 (2s)2 (2p). Its outer shell occupancy and chemical properties are similar to that of
Aluminium (Al), Gallium (Ga), Indium (In) and Thalium (Tl). These elements are often
used as p-type dopants (electron acceptors) in semi-conductors. The value of the total
angular momentum is j = l − s = 1/2 (due to spin-orbit coupling (see above) the state
THE CHEMICAL BOND 59
j = l + s = 3/2 has higher energy). Its outer electronic state is thus 2 P1/2 .
Carbon (C) has 6 electrons, two in orbital 1s, two in orbital 2s and two in orbital 2p.
Since orbital 2p is triply degenerate, the question arises as to where the two electrons
in 2p settle. Because of Pauli’s principle, electrons with identical wavefunction (i.e.
orbitals) have opposite spin, while electron in different orbitals may have similar spin.
Since electrons in different orbitals overlap and repel each other less, that situation is
energetically favorable giving rise to Hund’s rule: ”the state of highest spin has the
lowest energy”. Hence in Carbon the electrons in the 2p orbital have similar (parallel)
spin and occupy orbitals with different azymutal number m. The outer shell properties
of Carbon and its chemical properties are similar to Silicon (Si) and Germanium (Ge),
i.e. semiconductors. Tin (Sn) and Lead (Pb) have smaller band gaps (see above) and are
in fact conductors at room temperatures.
Nitrogen (N) has 7 electrons, two in orbital 1s, two in orbital 2s and three in orbital
2p. These outer electrons have parallel spin because of Hund’s rule and occupy the
three 2p orbitals with different azymutal number m. The outer shell occupancy and
chemical properties of Nitrogen are similar to that of Phosphorus (P), Arsenic (As),
Antimony (Sb) and Bismuth (Bi). These elements are often used as n-type dopants
(electron donors) in Si and Ge semi-conductors.
Oxygen (O) has 8 electrons, two in 1s, two in 2s and four in 2p. Two of those are
paired (they share the same orbital with opposite spin) and two have parallel spins and
share orbitals with different m. Its outer shell electron occupancy is identical to that of
Sulphur (S), Selenium (Se), Tellurium (Te) and Polonium (Po).
Fluorine (F) has nine electrons, the last five of which occupy the three 2p orbitals,
four are paired (they share the same orbital with opposite spin) and one occupy the
third orbital. The outer shell occupancy of Fluorine is similar to that of other Halogens:
Chlorine (Cl), Bromine (Br), Iodine (I) and Astatine (At).
Neon (Ne) has ten electrons which occupy all the 1s, 2s and 2p orbitals. All electrons
are paired and therefore not disponible for bonding. Neon like Helium and the other
Noble gases: Argon( Ar), Krypton (Kr), Xenon (Xe), Radon (Rn) have a similar outer
electron shell and share a very low chemical reactivity.
An interesting situation occurs when orbitals 4s and 5s fill up (for elements Ca and
Sr). The next ten elements have their electrons fill the more inner 3d or 4d shells. These
elements are known as transition metals. Similarly when orbitals 6s fill up (for Ba), the
next shell to fill up is the inner 4f shells which defines a set of 14 rare-earth elements
(Lanthanides) with similar chemical properties. Once this shell is filled the next one, 5d
is also an inner shell and the next ten elements share similar properties with transition
metals.
~2 2 e2 e2 e2
HΨ(~x, t) = − ∇ Ψ(~x, t) − ( + − )Ψ(~x, t) = En Ψ(~x, t) (2.70)
2me |~x + ~a| |~x − ~a| 2a
this equation can be solved by separation of variables (i.e. looking for a solution Ψ(µ, ν, φ) =
M(µ)N(ν)Φ(φ)) as was done for the hydrogen atom (in spherical coordinates). Noticing
that : |~x ± ~a| = a(cosh µ ± cos ν, we leave it as an exercise to the reader to show that
Eq.2.70 then yields the following equations:
∂2 Φ
+ m2 Φ = 0
∂φ2
∂2 M ∂M m2
+ coth µ + (2α cosh µ − + En0 sinh2 µ − λ)M = 0
∂µ2 ∂µ sinh2 µ
∂2 N ∂N m2
+ cot ν + (− 2 + En0 sin2 ν + λ)N = 0 (2.71)
∂ν 2 ∂ν sin ν
Where α ≡ 2a/r0 (with r0 = ~2 /me e2 , the Bohr radius of Hydrogen), En0 ≡ (2me a2 /~2 )(En −
e2 /2a) and m = 0, ±1, ±2, . . . and λ are quantum numbers (playing the role that m, l
played in the hydrogen atom). The energy levels En have been solved in 1927 (only one
year after Schroedinger solved the Hydrogen atom) by O.Burrau who then looked for
the distance 2a between the atoms that would minimize the ground state energy E0 .
Since most problems in physics are not exactly soluble and in particular the com-
putation of energy spectra of complex molecules, the existence of an exact solution for
H+2 was very helpfull in the development and testing of approximate methods to com-
pute eigen-energies and eigen-functions (orbitals) for more complex QM systems. One
of these approximation is known as the variational method (for details see L.P.Pauling
and E.B.Wilson, ”Introduction to quantum mechanics”, Chap.7). The idea is pretty sim-
ple. One assumes that in some limit a given problem can be solved exactly, i.e. a set
of eigen-functions can be computed for the Hamiltonian in that limit. One then uses a
linear superposition of these solutions as a trial function and one estimates the energy of
that state for the complete Hamiltonian. This energy is then minimized with respect to
the parameters of the superposition (for example the linear coefficients). Since one does
not expect the trial function to yield the exact solution of the full problem, the estimated
minimal energy Emin is an upper bound to the true energy of the system: Emin > E0 . In
general the more complete the set of functions used as a trial, the better the approxima-
tion. However the main problem with the variational approach is that there is no way of
THE CHEMICAL BOND 61
F. 2.18. The ground state energy level of the Hydrogen molecule ion H+2 as a function
of the distance R between the two protons. The exact solution E0 (R) is shown in
dashed and compared to the results obtained from the variational method for a sym-
metric and an anti-symmetric electronic wavefunction. Only the symmetric solution
describes a bound state (energy E s smaller than the hydrogen ground state energy
E1 ).
estimating how good an approximation it is. For that one needs to resort to perturbation
expansions, which we will study later.
In the case of the hydrogen molecule ion H+2 its Hamiltonian can be written as:
where HH is the Hamiltonian of the Hydrogen atom. When the two protons are far apart
(a r0 ) the solutions for the electron wavefunction are simply those computed for a
hydrogen atom centered on either proton, i.e. |Ψnlm (r1 ) > or |Ψnlm (r2 ) > with ~r1 = ~r − ~a;
~r2 = ~r + ~a. When the atoms are brought in proximity, we shall use for simplicity a trial
wavefunction |ΨT > which is a superposition of hydrogen 1s ground q states (with energy
E1 = −e2 /2r0 = −13.6eV) : |Ψ(r) >= R10 (r)Y00 (θ, φ) = exp(−r/r0 )/ πr03 :
We now have to determine the coefficients c1 , c2 that minimize E, i.e. for which ∂E/∂c1 =
∂E/∂c2 = 0. Taking the derivative of the previous equation with respect to c1 and c2
yields at the minimum of the energy a set of coupled homogenous equations:
H11 + H12
Es =
1+∆
H11 − H12
Ea =
1−∆
The first solution corresponds to a symmetric trial wavefunction: c1 = c2 :
1
|Ψ s >= √ (|Ψ(r1 ) > +|Ψ(r2 ) >)
2 + 2∆
The second solution corresponds to an anti-symmetric wavefunction: c2 = −c1 :
1
|Ψa >= √ (|Ψ(r1 ) > −|Ψ(r2 ) >)
2 − 2∆
The various integrals can then be evaluated numerically or in this case even exactly to
yield:
r0
H11 = E1 (1 − )+J
a
r0
H12 = ∆E1 (1 − ) + K
a
(2.73)
where J known as the Coulomb integral, K the resonance integral and ∆ the overlap
integral are:
THE CHEMICAL BOND 63
Z r
0 r0
J= d3 rΨ(r1 )(−e2 /r2 )Ψ(r1 ) = −2E1 − + e−4a/r0 (1 +
2a 2a
Z
2a
K= d3 rΨ(r1 )(−e2 /r2 )Ψ(r2 ) = 2E1 e−2a/r0 (1 + )
r0
Z 2
2a 4a
∆= d3 rΨ(r1 )Ψ(r2 ) = (1 + + 2 )e−2a/r0
r0 3r0
The energies of the symmetric and antisymmetric wavefunctions can then be recast as:
r0 J+K
E s = E1 (1 − )+ (2.74)
a 1+∆
r0 J−K
Ea = E1 (1 − ) + (2.75)
a 1−∆
Only the symmetric solution has a minimal energy E s = −15.36eV lower than E1 =
−13.6eV at an internuclear distance 2a ∼ 1.3Å. The anti-symmetric solution has an
energy Ea always larger than E1 and thus cannot represent a bound state of the H+2
ion. Comparing these values to the exact solution (E0 = −16.4eV at 2a = 1.06Å), see
Fig.2.18, suggests that in this case the simple variational approach yields a reasonable
approximation to the ground state of the system.
F. 2.19. The band gap ∆E of a few alkenes with n = 7, 9, 11 measured by the adsorp-
tion of photons of energy hν = ∆E. Notice that the measured energies are propori-
onal to sin π/(n + 1) as predicted from Hückel’ molecular orbital theory.
X
|Ψ MO >= ci |φi >
i
Just as we have done for H+2the idea is to determine the coefficients {ci } that minimize
the energy of the full Hamiltonian:
Neglecting the overlap between neighboring atomic orbitals, i.e. assuming: ∆ =< φi |φ j >'
0 one gets: X
ci c j Hi j − Ec2i δi j = 0
ij
Where Hi j =< φi |H|φ j >. Hii and Hi j are respectively the Coulomb and resonance inte-
grals we saw above. If only the overlap between nearest neighbours j = i ± 1 contribute
significantly to the resonance integral, minimization of the energy with respect to the
vector of coefficients {ci } yields:
E0 −A 0 . . . 0
c
c1
−A E −A . . . 0 1
0 . .
.. .. .. = E ..
(2.76)
. .
cn cn
0 . . . 0 −A
E0
THE CHEMICAL BOND 65
Where we defined: E0 ≡ Hii and A ≡ Hi,i+1 = Hi−1,i . Notice the similarity with the
model studied earlier for aromatic molecules, Eq.2.25. The eigen-energies can then be
computed as follows:
2 cos θ 1 0 . . .
0
1 2 cos θ 1 . . . 0
∆n = . = 0
..
. . . 0 1 2 cos θ
0
~2 ∂2 ~ 2 ∂2
H = −( + ) + V(|~r1 − ~r2 |)
2m1 ∂r12 2m2 ∂r22
Defining the center of mass (CM) coordinate : R ~ CM = (m1~r1 + m2~r2 )/(m1 + m2 )| and
~r12 = ~r1 − ~r2 allows to rewrite the previous Hamiltonian as: H = HCM + Hosc , where
HCM is the Hamiltonian of the center of mass (free particle of mass m1 + m2 ) and Hosc
is the Hamiltonian describing the two bound atoms in the CM coordinate system. Near
equilibrium the binding potential V(r12 ) can be expanded in a Taylor series:
1 ∂2 V ~ 2 + ...
V(r12 ) = V(d) − | (~r − d)
2 r12 =d 12
2 ∂r12
66 QUANTUM MECHANICS
F. 2.20. (a) The first eigen-functions of the harmonic oscillator. Notice the inversion
symmetry of the even function and the antisymmetry of the odd ones. (b) The com-
puted and measured eigenenergies of the vibrational spectrum of C6 H++ 4 (Vanoshi et
al., Theor. Chem. Account 120,45 (2008)). Notice the equal spacing of the spectral
lines and their value (∼ 0.1eV) typical of vibrational energies in molecules.
Defining k ≡ ∂2 V/∂r12
2
|r12 =d and looking at the deviations from equilibrium: ~r = ~r12 − d~
yields the Hamiltonian of an harmonic oscillator:
~ 2 ∂2 1
Hosc = − + kr2 (2.78)
2m ∂r2 2
with m = m1 m2 /(m1 + m2 ). The determination of the eigen-energies and eigen-functions
of a harmonic oscillator turns out to be one of those rare examples of an exactly soluble
problem in QM (the hydrogen atom is an other).
As done earlier, we shall look for a separable solution Ψ(x, y, z) = X(x)Y(y)Z(z) of
Schroedinger’s equation:
Hosc Ψ(x, y, z) = EΨ(x, y, z)
Since r2 = x2 + y2 + z2 we obtain:
∂2
X(x) + (λ x − α2 x2 )X(x) = 0 (2.79)
∂x2
√
with α = mω/~, ω = k/m and similar equations for Y(y) and Z(z). The eigenenergy is
given by:
~2 (λ x + λy + λz )
E=
2m
In the limit x → ∞, Eq.2.79, simplifies to X 00 = α2 x2 X, for which the asymptotic
bounded solution is X∞ ∼ exp(−αx2 /2). As we have done for the solution of the radial
equation of the Hydrogen atom, let us then look for a solution:
where f (x) is a finite polynomial. Inserting that Ansatz into Eq.2.79 yields:
THE CHEMICAL BOND 67
f 00 − 2αx f 0 + (λ x − α) f = 0
Looking for a polynomial solution: f (x) = n an xn yields the recursion:
P
~2 j( j + 1)
Ej = (2.87)
2I
The eigenfunctions are the spherical harmonics (see Appendix): Y jm (θ, φ) and as in the
Hydrogen atom, each eigenstate is 2 j+1 -fold degenerate (since m = − j, − j+1, ..., j). If
the molecule both vibrates and rotates its energy levels are only approximately a sum of
rotational and vibrational levels (in fact the system does not separates nicely into pure
vibrational and pure rotational modes).
For more complex molecules with different moments of inertia, the analysis be-
comes more complicated. For a symmetric top, i.e. if two of the moments of inertia are
equal (I1 = I2 , I3 , the Hamiltonian can still be written as:
[J1 , J2 ] = −iJ3
Notice the different sign as compared to the commutation relations of J~ ([J1 , J2 ] = iJ3 ).
These different angular momentum operators commute: [Ji , J j ] = 0 and satisfy J 2 =
J 2 . Hence the eigenstates of the symmetric top Hamiltonian are characterized by three
quantum numbers that define the eigen-values of J 2 (or J 2 ), J3 and J3 . For a given
eigenstate j, k of J 2 and J3 the eigen-energies are:
~2 ~2 1 1
E j,k,m = j( j + 1) + ( − )k2
2I1 2 I3 I1
When k > 0, the energy levels are 2(2 j + 1)-fold degenerate (the factor 2 j + 1 because
of the degeneracy in m (m = − j, ...., j) and the factor 2 because of the degeneracy
k → −k). The typical energies associated with molecular rotational levels corresponds
to microwave radiation energies (meV).
Hamiltonian H as the sum of a known exactly soluble one H0 plus a perturbation λH1 ,
where λ is a small parameter (λ 1):
H = H0 + λH1
One seeks the eigenstates |Ψn > of the full Schroedinger’s equation:
If these eigenstates span the Hilbert space of H (the space of its solutions) we may look
for an eigenstate of H as: X
|Ψn >= anm |φm >
m
Inserting that Ansatz into the full Schroedinger equation yields:
X X X X
anm H|φm >= anm (H0 + λH1 )|φm >= anm (m0 + λH1 )|φm >= anm En |φm >
m m m m
When λ = 0: En = n0 and |Ψn >= |φn >, i.e. anl = δnl . When λ 1 we will therefore
look for a solution as an expansion in λ:
At order λ we obtain:
X
|Ψn >= eλα |φn > +λ
(1)
nm |φm >
a(1)
m,n
The phase-shift by λα(1) is of no physical consequences (at this order it can be adsorbed
into a phase shift of |Ψn >) and can be chosen as zero. To second order in λ, Eq.2.90
yields:
X
when n = l : En(2) + En(1) a(1)
nn = < φn |H1 |φm > a(1)
nm
m
X
when n,l: (n0 − l0 )a(2)
nl = < φl |H1 |φm > a(1) (1) (1)
nm − E n anl
m
m,n
which yields:
1 X | < φm |H1 |φn > |2
nn = −
a(2)
2 m,n (n0 − m0 )2
One may compute higher order terms in this expansion, but usually only the first
non-zero contribution is computed. The advantage of this perturbation expansion over
TIME INDEPENDENT PERTURBATION THEORY 71
the variational approach seen earlier is that the error in a perturbation expansion up to
order n is of O(λn+1 ).
H = H0 + ezE
To first order the energy shift, Eq.2.90:
∆Enl
(1)
=< Ψnlm |eEr cos θ|Ψnlm >= 0
Indeed, using the mathematical identities:
l+1−m m l+m m
cos θ Pm
l (cos θ) = Pl+1 (cos θ) + P (cos θ) (2.93)
2l + 1 2l + 1 l−1
s s
(l + 1 + m)(l + 1 − m) (l + m)(l − m)
cos θ Ylm (θ, φ) = Yl+1,m (θ, φ) + Yl−1,m (θ, φ)
(2l + 3)(2l + 1) (2l + 1)(2l − 1)
≡ Cl+1,m Yl+1,m (θ, φ) + Cl−1,m Yl−1,m (θ, φ)
we may compute the first order energy shift (with |Ψnlm >= Rnl (r)Ylm (θ, φ)) as follows:
Z
∆Enl
(1)
= ∗
r2 drdΩRnl (r)Ylm (θ, φ)eEr cos θRnl (r)Ylm (θ, φ)
Z
= eE r3 drdΩR2nl (r)Ylm∗
(θ, φ)[Cl+1,m Yl+1,m (θ, φ) + Cl−1,m Yl−1,m (θ, φ)] = 0
where we used the orthogonality of the spherical harmonics (see Appendix). The second
order correction in the energy, Eq.2.91 is then:
X | < Ψnlm |eEr cos θ|Ψn0 l0 m > |2
(2)
Enl = (2.94)
n0 ,l0 ,n,l
nl0 − n00 ,l0
Notice that this sum is well defined only for non-Hydrogen atoms where the denom-
inator is non-zero (as argued above). In Hydrogen the degeneracy of the energy with
respect to the angular quantum number l necessitates a perturbation analysis specific for
degenerate eigenstates which we will present below. In view of Eq.2.93, we see that in
the sum the only terms that contribute have l0 = l ± 1. In fact since the lifting of the
l−degeneracy is a small effect with respect to the variation of the energy with the major
quantum number n, the main contribution in the sum appearing in Eq.2.94 will come
from levels n0 = n.
X | < Ψnlm |r cos θ|Ψnl0 m > |2
(2)
Enl = e2 E2
l0 =l±1
nl0 − nl0 0
Since the shift in the angular l-degeneracy is larger the smaller l is: nl0 − n,l−1
0
> n,l+1
0
−
nl0 > 0 and the energy shift Enl is in general negative, see Fig.2.21. This raising of the
(2)
F. 2.21. The shift in the spectral line of an alkaline, Rubidium excited to a high n
level (35s state). Notice the negative parabolic shift as a function of electric field,
from V.Bendkowsky et al., Nature, 458,1005 (2009).
F. 2.22. (a-b) Strong magnetic field lines pierce the surface of the Sun at its spots.
These are regions on the Sun’s surface that are cooler by about 1000◦ K than their
surrounding due to the damping of the underlying convective motion by the mag-
netic field. (c) This field of a few thousand Gauss causes the splitting of the spectral
emission lines measured along the vertical black line passing through a Sun’s spot
shown in (b).
Dirac’s equation yields the Schroedinger equation with a magnetic correction due to the
electron spin S~ with magnetic moment m~ = −(~e/2me c)~σ = −(eg/2me c)S~ , see Eq.2.57:
~ 2 Ze2
(~p + (e/c)A)
eg ~ ~
+ Ψ = EΨ
− §·B
2me r 2me c
~ ·A
In the Coulomb gauge: ∇ ~ = 0 (i.e. A
~ = (B~ × ~r)/2) this equation becomes:
~2 ∇2 Ze2 e2 ~ 2
( )
e ~ eg ~ ~
− − + A · ~p + A + § · B Ψ = EΨ
2me r me c 2me c2 2me c
In order to know what type of perturbation we need to consider let us estimate the
order of magnitude of the various terms on the left. The first two terms (the kinetic
and Coulomb energies) are of order of the ionization energy of the atom (typically 1-
10eV). The third term is of order ~eB/me c ' 10−8 B eV/Gauss, which for a strong
magnetic field B ∼ 104 Gauss is of O(10−4 eV). The fourth term on the left is of order
(e2 r02 /2me c2 )B2 ∼ 10−9 eV and is thus negligible with respect to the third one. The
Hamiltonian can thus be written as:
e ~ egB
H = H0 + ( B × ~r) · ~p + Sz
2mc 2me c
~ × ~r) · ~p = B
Since: ( B ~ · (~r × ~p) = B
~ · ~L, one obtains:
eB
H = H0 + (Lz + gS z )
2me c
Since H0 commutes with Lz (which eigenvalues are ~m; m = −l, ..., l) and with S z (with
eigenvalues ±~/2), the energy shift is:
e~B
∆E = (m ± 1) = ~ωL (m ± 1) (2.95)
2mc
where we set: g = 2 (see Eq.2.57). The frequency ωL = eB/2mc is known as the Larmor
frequency: it is the frequency of precession of a magnetic dipole about the direction of
the magnetic field. Notice that the magnetic field lifts the degeneracy in the azymuthal
quantum number m. It should also be noted that the present description of the Zeeman
effect is only an approximation valid for strong magnetic fields. Indeed as we have seen
when studying Dirac’s equation Lz and S z do not commute with the full Hamiltonian.
The reason that they do commute with H0 is that this Hamiltonian which we derived
from Dirac’s equation is only the lowest term in a low energy expansion of Dirac’s
relativistic Hamiltonian. In a strong magnetic field however, the magnetic perturbation
term is larger than the next (relativistic) terms in Dirac’s expansion which can thus
be neglected (for example the spin-orbit coupling discussed previously). The Zeeman
effect has been used to estimate the strong magnetic field coming out of the Sun’s spots
through the spliting of the Zeeman lines of Hydrogen atoms at the Sun’s surface, see
Fig.2.22
TIME INDEPENDENT PERTURBATION THEORY 75
Defining Vnm ≡ λ < φn |H1 |φm > yields the following equation:
+ V11 − En ...
0
V12 V1N
V21 0 + V22 − En . . . V2N
. . . . = 0 (2.96)
.. .. .. ..
... VN,N−1 0 + VNN − En
VN1
The solution of this N th order equation for En will usually yield N eigenvalues and N
orthogonal eigenstates ψn > which can then be used instead of the |φn > in a perturbation
expansion together with the other non-degenerate eigenstates of H0 .
Example: The Stark effect in Hydrogen.
When previously studying the response of atoms to a constant electric field E~ we
mentioned that the case of Hydrogen was particular since its energy levels are degen-
erate with respect to the quantum numbers l (and m) and thus the second order non-
degenerate perturbation expansion breaks down. We shall now see how the degeneracy
of the electronic energy levels in hydrogen are affected by the presence of an electric
field. The Hamiltonian is:
H = H0 + ezE
Consider the case of the n = 2 level of hydrogen for which the states: l = 0; m = 0
and l = 1; m = 0, ±1 all have the same energy: E2 = E1 /4 (with E1 = −13.6eV).
TIME DEPENDENT PERTURBATION THEORY 77
Following our previous perturbation analysis for degenerate energy levels, we need
to diagonalize the Hamiltonian matrix: < 2, l0 , m0 |H|2, l, m >. While the unperturbed
Hamiltonian H0 is diagonal with energy E2 , using Eq.2.93 we deduce that the dipole
coupling < 2, l0 , m0 |ezE|2, l, m > is non-zero only if m0 = m and l0 = l ± 1, i.e. only when
coupling states |2, 0, 0 > and |2, 1, 0 >. In that case:
Z Z
< 2, 1, 0|ezE|2, 0, 0 > = eE r drR21 (r)R20 (r) dΩY10 (θ, φ) cos θY00 (θ, φ)
3
= −3er0 E ≡ −∆E2
I
which solutions are: E so = E2 + ∆E2 = E2 + 3er0 E and E so
I
= E2 − ∆E2 with eigenstates:
|2, 0, 0 > −|2, 1, 0 >
|2, I > = √
2
|2, II >= |2, 0, 0 > +|2, 1, 0 >
√
2
III,IV
and E so = E2 with eigenstates |2, 1, 1 > and |2, 1, −1 >. Notice that for the hydrogen
atom the Stark effect, i.e. the shift in the energy level, is linear with electric field and
not quadratic as it is for the other atoms for which the electronic energy levels are non-
degenerate, see Eq.2.94.
i~∂t |Ψ(t) >= H|Ψ(t) >= H0 |Ψ(t) > +λH1 (t)|Ψ(t) > (2.97)
with initial condition: |Ψ(0) >= |φi >, we shall look for a solution as an expansion in
terms of the eigenstates of H0 :
78 QUANTUM MECHANICS
X
|Ψ(t) >= an (t)|φn >
n
Multiplying this equation on the left by < φm | and recalling that the eigenstates are
orthonormal: < φm |φn >= δmn yields:
dam (t) X
i~ = m0 am (t) + λ < φm |H1 (t)|φn > an (t)
dt n
0
Define: am (t) = µm (t)e−im t/~ to obtain the following equation for µm (t):
dµm (t) X 0 0
i~ =λ < φm |H1 (t)|φn > ei(m −n )t/~
dt n
Integrating yields:
λ X t
Z
µm (t) − δmi = dt < φm |H1 (t)|φn > eiωmn t µn
i~ n 0
with ωmn = (m0 − n0 )/~ and the initial condition µm (0) = δmi . For short enough times,
the system remains essentially in its initial state |φi > and for states m , i we may write:
λ t
Z
µm (t) ' dt < φm |H1 (t)|φi > eiωmi t
i~ 0
Now consider a periodic perturbation, such as an electro-magnetic wave, so that: λH1 (t) =
(Ve−iωt + V ∗ eiωt )/2 = |V| cos(ωt + θ):
< φm |V|φi > i[ωmi −ω]t < φm |V ∗ |φi > i[ωmi +ω]t
Z t
1
µm (t) ' dt e + e
i~ 0 2 2
= −[Vmi F(ω) + Vmi∗
F(−ω)]
The probability that the system is in state |φm > at time t is:
This transition probability will be large when either F(ω) or F(−ω) are large, which
occurs when m0 − i0 = ~ω or m0 − i0 = −~ω. The former case corresponds to absorption
TIME DEPENDENT PERTURBATION THEORY 79
of energy from the perturbing field (m0 > i0 ), the latter to emission of radiation from
the initial state (i0 > m0 ).
In case of adsorption the probability of finding the system in state |φm > at times t is
thus:
2π|Vmi |2
Pm (t) = |Vmi |2 |F(ω)|2 = |Vmi |2 (t/~)2 sinc2 [(ωmi − ω)t/2] → tδ(ωmi − ω) (2.98)
~2
where we used the mathematical identity: lima→0 sinc2 ax = (π/a)δ(x), which is a valid
approximation as long as (ωmi − ω)t < 1. Hence the transition rate from state |φi > into
state |φm >: T mi = dPm /dt is:
2π|Vmi |2 2π|Vmi |2 0
T mi = 2
δ(ωmi − ω) = δ(m − i0 − ~ω)
~ ~
Since the frequency of the initial beam is not infinitely sharp and if there exists a dis-
tribution of final state energies (which is usually the case due to Doppler broadening of
the final state energy, etc.) then the δ-function in the above
R equation has to be replace by
the energy density ρ(m ) of the final state (such that 1 = dδ( − i0 − ~ω) = dρ()):
R
2π|Vmi |2 0
T mi = ρ(m ) (2.99)
~
This equation is known as Fermi’s Golden rule. It relates the transition rate from the
ground state |φi > to the final state |φm > to this state’s energy density and to the coupling
between initial and final states. This is the result we obtained when studying the amonia
maser, see Eq.2.24.
In case of emission, the probability of finding the system in a lower energy state
|φm > after a time t is computed exactly as before:
∗ 2
2π|Vmi | 2π|Vmi |2 0
T mi = δ(m0 − i0 + ~ω) = ρ(i )
~ ~
which is the same result as that for adsorption (notice that here it is the energy density of
the initial state that appears in Fermi’s Golden rule, as the ground state being infinitely
lived is infinitely sharp). This is also in agreement with Einstein treatment of radiation,
see above.
Let us know investigate in more details the factors affecting the coupling element:
Vmi . Let the perturbation be a plane electromagnetic wave:
~=A
A ~0 ei(kx−ωt) + A
~∗0 e−i(kx−ωt)
propagating along the x-axis and let us choose the z-axis as parallel to A ~0 (which is
always possible unless some external field exist which defines the z-axis). The electric
80 QUANTUM MECHANICS
field is : E~ = −(1/c)∂t A
~ and B ~ × A.
~=∇ ~ The average intensity (Poynting vector) of this
electromagnetic wave is, see Eq.??:
I = (c/4π) < E~ × B
~ >= ω2 |A
~0 |2 /2πc
~2
Z
d i~
i~ < φm |z|φi > = < φm |[z, H]|φi >= < φm |pz |φi >= d3 xφm ∂z φi
dt m m
! !
d d d
but : i~ < φm |z|φi > = i~ < φm | z |φi > + < φm | z i~ |φi > = −(m0 − i0 ) < φm |z|φi >
dt dt dt
iqA0 ωzmi
Vmi =
c
And the transition rate is then:
2π|Vmi |2 2πq2 |A0 |2 ω2
T mi = 2
δ(ωmi − ω) = 2 |zmi |2 δ(ωmi − ω)
~ ~ c2
2πq 2
=( ) cI(ω) |zmi |2 δ(ωmi − ω) (2.100)
~c
The transition rate depends on the dipole moment between the initial and final states:
< φ f |qz|φi >. It is therefore known as the dipole transition rate. When investigating the
polarizability of atoms in a constant electric field by time independent perturbation the-
ory, see above, we have already been led to compute the transition element z f i between
TIME DEPENDENT PERTURBATION THEORY 81
various states |n, l, m > of the hydrogen atom, see Eq.2.94. We have seen there that this
element is zero unless m = m0 and l0 = l ± 1. If an other field (e.g. a constant mag-
netic field) exist, then the polarization of the EM-wave will in general be along an other
axis (say y) and the transition element will be non-zero if m0 = m ± 1. Therefore only
transitions between states differing in their angular momentum l by ±1 and in m by 0
or ±1 are possible (at leading order), for example transitions between s and p states are
possible, but not between two s or two p states.
functions are products of 1D-eigenstates). Using the property of the Hermite polynomi-
als:
2zHn = Hn+1 + 2nHn−1
It is easy to check that the dipole moment between initial and final states will be non-
zero only if: n0 = n ± 1.
Diatomic molecules can both vibrate and rotate. Their vibrational energy levels are
given by:
En1 ,n2 ,n3 = (n1 + n2 + n3 + 3/2)~ω
They are separated by an energy gap: ∆Evib = ~ω of O(0.1eV). The diatomic rotational
energy spectrum is:
~2 j( j + 1)
Ej =
2I
with a splitting between levels: ∆Erot = ~2 (2 j + 1)/2I of O(1meV) which is much
smaller than the energy gap between successive vibrational energy level. Electromag-
netically, i.e. light-induced transitions between vibrational-rotational energy levels in
diatomic molecules occur between vibrational levels with ∆n = ±1 and ∆ j = ±1.
Hence the emission spectrum from the first excited vibrational level to the ground state
will exhibit two bands known as R- and P-bands corresponding to transitions between
rotational energy levels differing by ∆ j = ±1, see Fig.2.24.
82 QUANTUM MECHANICS
F. 2.24. (a) Transitions between vibrational energy level n = 0 and n = 1 and rota-
tional energy levels differing by ∆ j = ±1 in a diatomic molecule such as CO. These
transitions define two characteristic spectral bands known as P-band when ∆ j = −1
and R-band when ∆ j = 1.