PHYSICAL CHEMISTRY I

Dr. Jhon Zapata Rivera

Assistant Professor
Department of Chemistry

e-Mail: jhon.zapata.rivera@correounivalle.edu.co
Of ce: Block E20, Floor 2nd, of ce 2080
Attention: Wednesday, 07:00-09:00

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 ATOMIC SPECTROSCOPY

• Quantum States for Many-Electron Atoms

• The Energy of a Con guration

• Spin-Orbit Coupling

• The Essentials of Atomic Spectroscopy

• Analytical Techniques Based on Atomic Spectroscopy

Bibliography:
1. Atkins P., Friedman R., Molecular Quantum Mechanics. 5th Edition, Ed. Oxford University Press
Inc., New York, 2011.
2. McQuarrie, D. A., Quantum Chemistry, 2nd Edition, University Science Books, New York, 2008.
3. Engel, T.; Hehre, W. J., Quantum Chemistry and Spectroscopy. 3th Edition. Pearson Education, Inc.
New York, 2013.
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 Quantum States for Many-Electron Atoms
The quantum numbers n , l , ml , and ms that were used to characterize eigenfunctions for the
H atom are associated with the eigenvalues of the operators Ĥ , l 2̂ , l ẑ , and sẑ .
These quantum numbers are good quantum numbers because its operators commutes.
However, n, l, ml, and ms are not good quantum numbers for any many-electron atom or ion.
Good quantum numbers for many-electron atoms are generated by forming vector sums of
the electron orbital and spin angular momenta separately, L and S , which have the z
components ML and MS:
∑ i ∑ i
L= l and S = s
i i

where the summation is over the electrons in un lled subshells. The magnitudes of L and S
are L(L + 1)ℏ and S(S + 1)ℏ, respectively.

We next discuss many electron-atom operators L̂ , L̂ z, S,̂ and Sẑ , which are formed from one-
electron operators, resultant for all electrons in un lled subshells of the atom.

2 2

( i ) (∑ )
Sẑ = ̂ S2̂ = sî L̂ z = ̂ L̂ 2 = l î
∑ ∑
sz,i and
∑
l z,i and
i i i

in which the index i refers to the individual electrons in un lled subshells. The good quantum
numbers for many-electron atoms for Z < 40 are L, S, ML and MS.
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 Quantum States for Many-Electron Atoms
The occupied orbitals of an atom are speci ed in a con guration. For example, the electron
con guration of Ne is 1s 22s 22p 6.
Considering the electron-electron repulsion and invoking the Pauli exclusion principle splits
a con guration into terms. A term is a group of states that has the same L and S values.

Example Problem 1:
Is ψ(1,2) = 1s(1)α(1)1s(2)β(2) − 1s(2)α(2)1s(1)β(1) an eigenfunction of the operator Sẑ ? If so,
what is its eigenvalue MS?
Sẑ = sẑ (1) + sẑ (2) , where sẑ (i) acts only on electron i

Sẑ ψ(1,2) = (sẑ (1) + sẑ (2))[1s(1)α(1)1s(2)β(2) − 1s(2)α(2)1s(1)β(1)]

ℏ ℏ ℏ ℏ
= [1s(1)α(1)1s(2)β(2)] + [1s(2)α(2)1s(1)β(1)] − [1s(1)α(1)1s(2)β(2)] − [1s(2)α(2)1s(1)β(1)]
2 2 2 2

(2 2)
ℏ ℏ
= − [1s(1)α(1)1s(2)β(2) − 1s(2)α(2)1s(1)β(1)] = 0 × ψ(1,2)

This result shows that the wave function is an eigenfunction of Sẑ with MS = 0.
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 The Energy of a Con guration
Consider the excited state of He with the con guration 1s 12s 1. Because both electrons have
l = 0, | L | = 0. We next show that there are two different values of | S | in consistency.
Adding the scalar components ms for the 2 electrons in each of the four possible
combinations gives the values MS = ms1 + ms2 = 0 twice, as well as MS = + 1 and MS = − 1.

Since MS takes integer values between +S and −S, the S = 1 group must include MS = 0, + 1,
and −1. The one remaining combination has MS = 0, which is only consistent with S = 0.

Because of the number of possible MS values, the S = 0 spin combination is called a singlet
(2S + 1 = 1) and the S = 1 spin combination is called a triplet (2S + 1 = 3).
Now that we know the S values for the four spin combinations, we can write antisymmetric
wave functions for He 1s 12s 1 that are eigenfunctions of S2̂ with S = 0 and S = 1.
1 1
S = 0 ϕsinglet = [1s(1)2s(2) + 1s(2)2s(1)] [α(1)β(2) − β(1)α(2)]
2 2

1 1
S = 1 ϕtriplet = [1s(1)2s(2) − 1s(2)2s(1)]α(1)α(2) or [1s(1)2s(2) − 1s(2)2s(1)]β(1)β(2)
2 2
1 1
or [1s(1)2s(2) − 1s(2)2s(1)] [α(1)β(2) + β(1)α(2)]
2 2 5
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 The Energy of a Con guration
Quantum states that have the same values for L and S but different values of ML and MS is
degenerate in energy.
Such a group of states is called a term, and the L and S values for the term are indicated by
the term symbol 2S+1L. Terms with L = 0, 1, 2, 3, . . . are given the symbols S, P, D, F, . . .
There are 2L + 1 quantum states (different ML values) for a given value of L and the 2S + 1
states (different MS values) for a given value of S.
Thus, a term will include (2L + 1)(2S + 1) quantum states, all of which have approx. the same
energy. This is the degeneracy of a term. The superscript 2S + 1 is called the multiplicity.
Consider the following examples:
1. For the He atom with 1s 2 con guration (as well as lled subshell or shell).
• ML = 0 and MS = 0 are only consistent with L = 0 and S = 0. It is characterized by the term 1S.
2. For a C 1s 22s 22p 13d 1 con guration (or whatever p 1d 1 ) where an electron has been
excited from the 2p to the 3d orbital. Only the 2p and 3d e- need to be considered.
• The possible values of L and S are given by the Clebsch–Gordon series. The allowed L values are given
by l1 + l2, l1 + l2 − 1, …, | l1 − l2 | . The allowed S values are s1 + s2 and s1 − s2.
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• Since, l1 = 1 and l2 = 2, and s1 = s2 = 2 , L can have the values 3, 2, and 1, and S can have the values 1
and 0. We conclude that the1s 22s 22p 13d 1 con guration generates 3F, 3D, 3P, 1F, 1D, and 1P terms.
• The degeneracy of these terms, (2L + 1)(2S + 1), is 21 , 15 , 9 , 7 , 5 , and 3 , respectively, which
corresponds to a total of 60 quantum states.
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 The Energy of a Con guration
Consider the following examples:
3. For the C atom with 1s 22s 22p 2 con guration. To determine the possible terms consistent
with a p 2 con guration, it is convenient to display the information:

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 The Energy of a Con guration
Example Problem 2:
What terms result from the con guration s 1d 1 ? How many quantum states are associated
with each term?

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 The Energy of a Con guration
The same procedure can be followed for any con guration and a few examples are shown in
next table for electrons in the same shell:

The numbers in parentheses behind the term symbol indicate the number of different terms
of that type that belong to the con guration.
Note that con gurations with a single electron or hole in the un lled shell or subshell give
only a single term as discussed earlier.
In lled shells or subshells, ML = MS = 0 because ml and ms take on all possible values
between their maximum positive and negative values. For this reason the term symbol for s 2,
p 6, and d 10 is 1S.

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 The Energy of a Con guration
From the examination of a large body of spectroscopic data, Friedrich Hund deduced Hund’s
rules, which state that for a given con guration the following are true:

RULE 1
The lowest energy term is that which has the greatest spin multiplicity. For example, the 3P
term of an np 2 con guration is lower in energy than the 1D and 1S terms.

RULE 2
For terms that have the same spin multiplicity, the term with the greatest orbital angular
momentum lies lowest in energy. For example, the 1D term of an np 2 con guration is lower
in energy than the 1S term.

Hund’s rules predict that in placing electrons in one-electron orbitals, the number of
unpaired electrons should be maximized. This is why Cr has the con guration [Ar]4s 13d 5.
Hund’s rules imply that the energetic consequences of electron–electron repulsion are
greater for spin than for orbital angular momentum.
It is straightforward to predict the lowest energy term among the possible terms using the
following: L and S for the lowest energy term are given by L = ML,max and S = MS,max.

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 The Energy of a Con guration
Example Problem 3:
Determine the lowest energy term for the p 2 and d 6 con gurations.

For the p 2 con guration, ML,max = 1 and MS,max = 1. Therefore, the lowest energy term is 3P.
For the d 6 con guration, ML,max = 2 and MS,max = 2. Therefore, the lowest energy term is 5D.

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 Spin-Orbit Coupling
Electrons have nonzero magnetic moments if L > 0 and S > 0. The separate spin and orbital
magnetic moments can interact by spin-orbit coupling, just as two bar magnets interact.
Under these conditions, the operators L̂ 2 , L̂ z , S2̂ , and Sẑ no longer commute with Ĥ , but the
operators J 2̂ and Jẑ do. Thus, J is the total angular momentum de ned by
J=L+S
The magnitude of J can take on all values given by J = L + S , L + S − 1 ,…, | L − S | and MJ
can take on all values between zero and J that differ by one.
All quantum states with the same J value have the same energy and belong to the same level.
The quantum number J is included in the nomenclature for a level as a subscript, (2S+1)LJ.
In a magnetic eld, states with the same J , but different MJ , have different energies. All of
these effects are observable in spectroscopies as shown for carbon

Taking the dependence of the electron repulsion on

the directions of L and S into account splits the
con guration into terms of different energy as shown.
Taking the coupling of L and S into account leads to a
further splitting of the terms into levels according to
the J values as shown on the right.
The separation of the levels for the 3P term has been
multiplied by a factor of 25 to make it visible.

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 Spin-Orbit Coupling
If the coupling is suf ciently large as in atoms for which Z > 40 , the only good quantum
numbers are J and MJ. For example, the 3P term has J values of 2, 1, and 0.
In counting, 2J + 1 states with different MJ values are associated with each J value. This gives
ve states associated with 3P2. Taking spin-orbit coupling into account gives Hund’s third rule:

RULE 3
The order in energy of levels in a term is given by the following:
• If the un lled subshell is exactly or more than half full, the level with the highest J value has the
lowest energy.
• If the un lled subshell is less than half full, the level with the lowest J value has the lowest energy.
Therefore, the 3P0 level has the lowest energy for an np 2 con guration. The 3P2 level has the
lowest energy for an np 4 con guration, which describes the O atom.

Example Problem 4:
What values of J are consistent with the terms 2P and 3D ? How many states with different
values of MJ correspond to each?
For the 2P term, L = 1 and S = 1/2 .Therefore, J can have the values 3/2 and 1/2 . There are
2J + 1 values of MJ, or 4 and 2 states, respectively.
For the 3D term, L = 2 and S = 1 . Therefore, J can have the values 3 , 2 , and 1 . There are
2J + 1 values of MJ or 7, 5, and 3 states, respectively.
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 The Essentials of Atomic Spectroscopy
Not all transitions between states are allowed, there are some rules that specify the speci c
transitions that may occur.
The interpretation of spectra requires knowledge of the selection rules for the spectroscopy
being used. Selection rules can be derived based on the dipole approximation.
Selection rules are established by identifying the conditions under which the transition
dipole moment is ≠ 0 (for an allowed transition) or 0 (for a forbidden transition).
The transition dipole moment (μ) for a transition between states | i⟩ and | f ⟩ is de ned as

μfi = ⟨ f | μ | i⟩

where μ = − er is the electric dipole operator.

Large shifts of charge through large distances can deliver strong impulses provided they have
a dipolar character and such transitions give rise to intense lines.
For instance, in the transition between s - and p -orbitals but not between s -orbitals where
the shift of charge is spherically symmetrical.

We shall now see that transition dipole moment entails three constraints on the transitions
that may occur: on parity, on Δl, and on Δml.

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 The Essentials of Atomic Spectroscopy
Based on group theory μfi must be zero unless the integrand in ⟨ f | μ | i⟩ is totally symmetric
under the symmetry operations of the system, which for atoms is the full rotation group, R3.

The easiest operation to consider is inversion, under which r → − r . Under inversion, an

atomic orbital with quantum number l has parity (−1)l.
Orbitals with even l (s- and d -orbitals for example) do not change sign whereas those with
odd l (p- and f-orbitals for example) do change sign.
The parity of the integrand ⟨ f | μ | i⟩ is therefore (−1)lf (−1)(−1)li , which is even if the two
orbitals have opposite parity (one odd, the other even).
This argument is the basis of the Laporte selection rule:
• The only allowed electric-dipole transitions are those involving a change in parity.
However, we have already ruled out transitions that do not change parity, so the only
allowed transitions are those to the states with lf = li ± 1. That is:

Δl = ± 1

The basis of the Δl = ± 1 selection rule is the conservation of

angular momentum and the fact a photon has a helicity (the
projection of its spin on its direction of propagation) of ±1.
Note that the absorption of a photon can result in either an
increase or a decrease of 1.
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 The Essentials of Atomic Spectroscopy
Now we need to know that a photon has an intrinsic helicity, σ, the spin angular momentum
relative to its line of ight, of σ = ± 1.

The change in ml that accompanies the absorption or emission

of a photon; the z -axis is taken to be the line of ight of the
photon.

Then, absorption of a left-circularly polarized photon (with helicity σ = + 1 ) results in

Δml = + 1 to preserve overall angular momentum, and its emission results in Δml = − 1.
The opposite holds for a right-circularly polarized photon. The maximum change in ml is
therefore ± 1.
An allowed intermediate value may also occur if the photon is traveling in an intermediate
direction. Therefore, the general selection rule is
Δml = 0, ± 1

The dipole selection rules for atomic transitions are Δl = ± 1 , and ΔL = 0, ± 1 , and
ΔJ = 0, ± 1. There is an additional selection rule, ΔS = 0, for the spin angular momentum.
Note that the rst selection rule refers to the angular momentum of an electron involved in
the transition, whereas the other rules refer to the vector sums for all electrons in the atom.
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 The Essentials of Atomic Spectroscopy
Example Problem 5:
Calculate the electric dipole transition moment for the transition 2s → 2pz in a hydrogenic
atom for z-polarized radiation.

We will use the de ned wave functions to evaluate the integral ⟨2pz | μz | 2s⟩ with
μz = − er cos θ. The wave functions for the orbitals are

1/2

( 32πa05 )
5
Z
ψ2pz = r cos θe−Zr/2a0

1/2

( 32πa05 )
3
Z −Zr/2a0
ψ2s = (2a − Zr)e

The integral we require is therefore

∞ π 2π

( 32πa0 ) ∫0
Z4 3ea0
∫0 ∫0
4 −Zr/2a0 2
⟨2pz | μz | 2s⟩ = − e (2a − Zr)r e dr cos θ sin θdθ dφ = −
5 Z

The physical observable, the transition intensity, depends on the square modulus of the
transition dipole moment.
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 The Essentials of Atomic Spectroscopy
The spectrum of atomic hydrogen arises from transitions between its permitted states.
The difference in energy, ΔE, between the states is discarded as a photon of energy hv and
wavenumber v̄, where v̄ = v/c.
Ignoring the spin, the state of an electron in a hydrogen atom is speci ed by three quantum
numbers, n, l, and ml and its energy is given by
hcRH μe 4
En = − 2 ; RH = 2 3
n 8ε0 h c

where RH is the Rydberg constant for hydrogen. For the transition n2 → n1, the wavenumber
of the emitted radiation is

( n1 n2 )
1 1
v̄ = 2
− 2 RH

For a given value of n1, the set of transitions from n2 = n1 + 1, n1 + 2,... constitutes a series
of spectral lines. These series bear the names of their discoverers or principal investigators:

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 The Essentials of Atomic Spectroscopy
E → 0 when n → ∞ , and corresponds to the complete removal of the electron from the
atom; that is, n = ∞ corresponds to the ionized state of the atom.
The ionization energy I of the atom, the minimum energy required to ionize it from its
n = 1 ground state, is the energy difference E∞ − E1. Hence,
I = hcRH

To a good approximation, we can use me in place of μ and, subsequently, use the value of R∞
reported in the literature. Therefore, in general,
I = hcZ 2 R∞

and the ionization energies of hydrogenic atoms scale as Z 2 . Thus, the ionization energy of
He+ is 4 × 13.60 eV = 54.40 eV.
Information from atomic spectra is generally displayed in a standard format called a Grotrian
diagram. An example is shown for He, for which L + S coupling is a good model.

The ground and the rst few excited states of the He

atom are shown on an energy scale.
Several, but not all, allowed (solid lines) and forbidden
(dashed lines) transitions are shown.

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 Analytical Techniques Based on Atomic Spectroscopy
The absorption and emission of light that occurs in transitions between different atomic
levels provides a powerful tool for qualitative and quantitative analysis of chemical samples.

In atomic emission spectroscopy (AES) the light emitted by excited atoms as they undergo
transitions back down to the ground state is dispersed into its component wavelengths by a
monochromator and the intensity of the radiation is measured as a function of wavelength.

The emitted light intensity is proportional to the number of excited-state atoms and the
wavelengths at which emission occurs are characteristic for the atom.
The technique can be used for both qualitative and quantitative analysis.
Temperatures in the range of 1800 to 3500 K can be achieved in ames and carbon furnaces
and up to 10,000 K can be reached in plasma arc sources.

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 Analytical Techniques Based on Atomic Spectroscopy
Atomic absorption spectroscopy (AAS) differs from AES in that light is passed through the
heated zone and the absorption associated with transitions from the lower to the upper
state is detected.

Because this technique relies on the population of low-lying rather than highly excited
atomic states, it has some advantages in sensitivity over atomic emission spectroscopy.
It is a very widely used technique because the sensitivity would be greatly enhanced if the
light source were nearly monochromatic with a wavelength centered at λtransition.

The intensity of light as a function of its

frequency is shown at the entrance to the heated
zone and at the detector for broadband and
monochromatic sources.
The absorption spectrum of the atom to be
detected is shown in the middle column.

To detect the absorption, the light needs to be dispersed with a grating and the intensity of
the light must be measured as a function of frequency.
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 Analytical Techniques Based on Atomic Spectroscopy
Example Problem 6:

The 2S1/2 → 2P3/2 transition in Na has a wavelength of 589.0 nm. This is one of the lines
characteristic of the sodium vapor lamps used for lighting streets, and it gives the lamps their
yellow-orange color.
Calculate the ratio of the number of atoms in these two states at 1500, 2500, and 3500 K,
based on the Grotrian diagram for Na in which the transition of interest is shown as a blue
line:

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 Analytical Techniques Based on Atomic Spectroscopy
Example Problem 6:

The 2S1/2 → 2P3/2 transition in Na has a wavelength of 589.0 nm. This is one of the lines
characteristic of the sodium vapor lamps used for lighting streets, and it gives the lamps their
yellow-orange color.
Calculate the ratio of the number of atoms in these two states at 1500, 2500, and 3500 K.
The ratio of atoms in the upper and lower levels is given by the Boltzmann distribution:
nupper gupper
= e −ΔE/kBT
nlower glower

The degeneracies g are given by 2J + 1, which is the number of states in each level:
3 1
gupper = 2 × + 1 = 4 glower = 2 × + 1 = 2
2 2
From the Boltzmann distribution, it follows that:
nupper gupper nupper 4 − (16.626 × −9
10−34 Js)(212.998 × 108ms−1
= e −hc/λtranskBT then = e (589.0 × 10 m)(1.381 × 10−23JK−1) × T
nlower glower nlower 2

Leading to 1.699 × 10−7 at 1500 K, 1.145 × 10−4 at 2500 K, and1.866 × 10−3 at 3500 K

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