Electronic Spectroscopy

Analysis of the spectrum of diatomic molecules shows that in an electronic state, there
are a large number of vibrational levels and in each vibrational level there are numerous
rotational energy levels also. The separation between two consecutive electronic states is of the
order of 106cm-1 or more and the transitions between them lie in the visible or UV regions of the
electromagnetic spectrum. During an electronic transition, changes in the vibrational as well as
rotational energy levels also can take place. For an electronic spectrum, there is a change in the
electronic state. Molecules having permanent electric dipole moment produce pure rotational
spectrum. Vibrational spectrum requires change of dipole moment during its normal mode of
vibration.

The Born–Oppenheimer approximation

Electrons and nuclei in a molecule experience same forces of magnitude but nuclei ~ 4
times more massive, so electrons move much more rapidly. Energy of a molecule depends on the
relative positions of nuclei. Born-Oppenheimer Approximation is that nuclear and electronic
motion are separable and independent (reasonable as nucleus moves much slower).

According to Born-Oppenheimer approximation, the electronic, vibrational and

rotational energies of molecules are independent of each other. So the total energy can be
expressed as:

Etotal= Eelec + Evib+ Erot

A change in the total energy of molecule may then be written as;

ΔEtotal= ΔEelec + ΔEvib+ ΔErot (J)

In terms of wavenumber it is written as;

Δ ϵ total=Δ ϵ elec + Δ ϵ vib + Δ ϵ rot (cm-1)

The approximate order of their magnitudes are given by;

ΔEelec ≈ ΔEvib x 103 ≈ ΔErot x 106

So the vibrational level changes will produce a coarse structure and rotational
level transitions will produce a fine structure in the electronic spectrum. So the spectrum
is called electronic- vibrational- rotational spectrum.

Electronic spectrum can be given by all types of molecules since changes in

electronic distribution involved in electronic level. Changes can cause a change in dipole
moment. This means that homo nuclear molecules (for eg; H 2 or N2), which show no
rotation or vibration- rotation spectra, do give an electronic spectrum and show rotational
structure in their spectra from which rotational constants and bond vibration frequencies
may be derived.

Vibration Coarse structure

In order to understand the Vibration Coarse structure of a molecule,let us drop the

rotational energy terms from expression of total energy as;

ϵtotal= ϵelec + ϵvib

2 −1
ϵ total=ϵ elec +(V +1/2)υ e – x e (V +1 /2) υ e cm .

Where ‘V’ is the vibrational quantum number with values 0,1,2,3 etc, υ e is the oscillation
frequency of the molecule and xe is its anharmonicity constant.
ϵ elec isthe energy of the electronic state .

Let V’’ and V’ be the vibrational levels of the lower and upper electronic states
respectively. There are no selection rule for V’’→ V’ transition. Vibrational level
transitions may or may not take place. Every V’’→ V’ transition may take place and
large number of spectral lines would be expected following a specific electronic

transition.

Using the equation discussed, the frequency of a spectral line is given by

υ v ,v } = left ({{ϵ} ^ {'}} rsub {elec } - {{ϵ} ^ {”}} rsub {elec } right ) + left [left ({V} ^ {'} + {1} over {2} right ) {overline {{υ} rsub {e}}} ^ {'} –
'
{{left ({V} ^ {'} + {1} over {2} righ

A change in vibrational Q. number accompanying an electronic transition does not follow

any selection rules of vibrational spectroscopy. That is all the (v’’→v’) transitions are
possible. Since most of the molecules are present in the ground vibrational energy state,
the transitions from this level are of considerable energy. The transitions which originate
from v’’= 0 state, labeled according to their (v’’,v’) values as (0,0), (1,0), (2,0), (3,0) are
of large intensity. The set of lines corresponding to these transitions are known as v’
progression as the value of v’ increases by unity for each line in the set. The wavenumber
of (0,0) transition is
1 1 1 1
υ (0,0) = ( ϵ elec −ϵ )+ 2 υ '
' ”
elec − υ ' e x ' e− υ ' ' + υ ' ' e x ' ' e
e 4 2 e 4

On the high frequency side, there will be crowding of lines. The above eqn shows that the
observation of few lines in a band enables one to calculate the vibrational frequency
υ e ∧anharmonicity constan t x e of both the ground as well as excited electronic states of a
molecule addition to the separation between the electronic states.

Franck-Condon principle

The Franck-Condon principle states that: an electronic transition takes place

sufficiently rapidly that the nuclei do not change their internuclear positions during the
transition. Consequently, when energy is absorbed in an electronic transition, the nuclei
suddenly find themselves in a new force field and at positions which are not in equilibrium for
the new electronic state. This is shown schematically in Fig. 1, in which an electronic absorption
from the ground state appears as a vertical line because of the Franck-Condon principle. The
internuclear separation of the ground state becomes a turning point, the extent of maximum
displacement, in a vibration of the excited state. The vertical transition has the greatest
transition probability but transitions to nearby vibrational levels also occur with lower
intensity. Therefore, instead of an electronic absorption occurring at a single, sharp line,
electronic absorption consists of many lines each corresponding to the stimulation of different
vibrations in the upper state. This vibrational structure (or progression) of an electronic
transition can be resolved for small molecules in the gas-phase, but in a liquid or solid collisional
broadening of the transitions cause the lines to merge together and the electronic absorption

spectrum is often a broad band with limited structure.

Rotational fine structure of electronic-vibration spectra

 Under high resolution of electronic spectra, each line in the spectrum
consists of a set of closely spaced lines caused by the rotational fine structure of
electronic-vibration transitions. The total energy according to Born –Oppenheimer
approximation is;

Δϵtotal= Δϵelec + Δϵvib+ Δϵrot (cm-1)

υ spec = υ (V’,V”) + Δϵrot

Where υ (V’,V”) represents total wave number for electronic and vibrational transitions.

Selection rules for rotational transitions depend on the type of electronic transitions.

(i) If both upper and lower electronic states have angular momentum about the
bond axis, the rule is ΔJ = 0,±1, but J=0 to J=0 transition is not allowed.

J=0 ≠ J=0
(ii) If the upper and lower electronic states have no angular momentum about the
inter nuclear axis, ΔJ =±1where J is the rotational quantum number.
In the second case only ‘P’ and ‘R’ branches appear in the rotational fine
structure while in the first case, P,Q and R branches appear. The wavenumber υ
(V’,V”) is known as the Band origin.

υ spec = υ (V’,V”) + Δϵrot = υ (V’,V”) + B’J’(J’+1) – B”J’’(J’’+1)

Where J’’ and B’’ are the rotational level and rotational constant in the lower
electronic state and J’ and B’ are the corresponding values in the upper electronic
state.
Taking the P,R and Q branches in turn;
1) P Branch: ΔJ = -1, J’’=J’+1
Δϵ = υ P = υ (V’,V”) – (B’+B’’)(J’+1) + (B’-B”)(J’+1)2cm-1 where J’ = 0,1,2,...
2) R Branch: ΔJ = +1, J’=J’’+1
Δϵ = υ R = υ(V’,V”) + (B’+B’’)(J’’+1) + (B’-B”)(J’’+1)2cm-1 where J’ = 0,1,2,...
These two equations can be combined into
υ P,R = υ (V’,V”) + (B’+B’’)m + (B’-B”)m2 cm-1 where m = ±1, ±2,...

Positive values of ‘m’ refer to R branch where ΔJ = ±1and negative values of ‘m’
refer to P branch, where ΔJ = -1, ‘m’ cannot be zero.
For the Q Branch, ΔJ = 0; J’ = J’’
υ Q = υ (V’,V”) + (B’-B’’)J’’+ (B’-B”) J’’2cm-1 where J’’= 1,2,3... (0 to 0 transitions
are not allowed).
 Coming back to P and R branches, it is observed that P branch appears on
the left hand side of the band centre and the spacing increase with increases in the
‘m’ value. The R Branch appears on the right hand side of the band origin and the
spacing decreases with increasing ‘m’ value so rapidly that after reaching a
maximum value of wave number the spectral lines return to lower wave numbers.
The point at which the return occurs ie, where the spacing becomes zero is called
‘band head’.

In this case where B’ < B’’ the band head appears in the R branch on the higher
wave number side of band centre, such a band is said to be degraded or shaded
towards the red. ie, the tail of the band points towards the low frequency side.
 If electrons excited are form antibonding molecular orbitals, bonding
becomes stronger and internuclear distance decrease in the excited state. So
B’>B’’ and hence the spacing increases with the increasing ‘m’ values in the ‘R’
branch. In the P branch, spacing decrease with increase in ‘m’ value reaches the
band head and returns to higher frequency side or the rotational fine structure is
shaded to the right or violet.

Fortrat Parabolas

Wavenumbers of lines in P, R and Q branches can be expressed with continuous variables p and q as

υ P,R = υ (V’,V”) + (B’+B’’)p + (B’-B”)p2…………………………………(1)

υ Q = υ(V’,V”) + (B’-B’’)q+ (B’-B”) q2………..………………………….(2)

Where p takes both positive and negative values whereas q takes only positive values.Equations
(1) and (2) are equations of parabolas .These parabolas are known as the Fortrat parabolas.The
PR parabola intersects the axis at N, the band origin. Its vertex H is the band head of the band.
Since we have a turning point at the vertex, we have

d ϑ P ,R
= ( B + B ) + 2 ( B −B ) p=¿0
' '' ' ''
dp

Thus, the position of the band head corresponds to

' ''
(B +B )
Phead = ˗ ………………………………………………………….(3)
2(B ' −B ' ' )

Using equation (3) in (1), we have

'' 2
ϑ P , R−υ(V’,V”) = −( B + B )
'

4¿¿

For B’˂ B” ,the right side is positive. Thus the head of a band is at a higher wave number than
the band origin. This shows that the band head appears in the R branch with positive p values.
When B’˃ B”, the band head occurs in the P branch with negative p values.
Dissociation

At absolute zero, the energy of a molecule is the one contributed by the vibrational zero point
energy ϵo (cm-1). The amount of energy required to break a stable molecule AB in the υ = 0 vibrational
state into two atoms A and B, each in the G.S, is known as the dissociation energy D 0. The figure given
shows dissociation energies Do” and Do’ of the G.S and E.S of molecules, respectively. The equilibrium
dissociation energy De is related to Do as

De = Do + ϵo (cm-1)

Normal electronic spectra of a diatomic molecule consists of a series of vibrational transitions with or
without rotational fine structure and then a continuum. The lower end of the continuum gives the energy
required to produce dissociation with zero kinetic energy for the dissociation products (atoms). Generally
a molecule in the state corresponding to the continuum limit dissociates into a normal atom and an excited
atom with excitation energy E ex. This Eex is the total energy of the dissociation products in the upper state
(photo-dissociation by excitation) minus the total energy of the dissociation products in the lower state.
When the molecule dissociates from one of the continuum states, the energy in excess of continuum limits
appears as kinetic energy. Thus;

υ cont limit =D } rsub {o} + {E} rsub {ex ¿

Further
υ cont limit =υ00 + Do '

Therefore
D } rsub {o} = {overline {υ}} rsub {00} + {D} rsub {o} ' - {E} rsub {ex ¿
Value of υ cont limit isknown from electronic spectroscopy whereas the value of Eex is known from atomic
spectroscopy. After using these values, one can calculate the dissociation energy.

The vibrational energy ϵv of a diatomic molecule is

2
ϵv = (v+1/2)υ e - (v+ 1/2) υe x e

The separation Δϵ between two successive vibrational states is

Δϵ = ϵv+1- ϵv = υ e [1−2 x e ( v +1 ) ]

The separation decreases linearly with the increase of

v∧tends ¿ zero at the dissociation limit . Denotingthe value of v as v max corresponding to the

dissociation limit (Δϵ=0) we have;

υ e [ 1−2 x e ( v max +1 ) ]=0

1
v max= −1
2 xe

The vibrational energy for v=v max is the dissociation energy De. Thus we have

( ) ( )
2
1 1 1 1
De = − υe− − υe xe
2 xe 2 2 xe 2
 υe 1 υe
= − υe xe ≈ cm-1
4 xe 4 4 xe

For the known values of υ e ∧x e, the value of De can be obtained and finally the value of
D } rsub {o} can be calculated ¿

Predissociation

A continuum on the high wavenumber side in electronic spectra corresponds to ordinary dissociation.
However in certain cases the rotational fine structure is diffused or a continuum is observed for
intermediate changes as shown in the fig. Occurrence of such diffuse structure or a complete continuum
below the true dissociation limit is known as predissociation.

A simple case of predissociation may be understood with respect to the Morse curves X,A and B as
shown above. Here the excited state B is not stable as it has no minimum. Let us consider a transition
from the curve X to A. In some cases it is possible to cross over to the curve B and this leads to the
molecule to dissociate. When this radiationless transition occurs from the curve A to B, there is no
rotation of the molecule as the time required for a molecular rotation is 10 -10s. However the vibrational
energy whose structure is quantized, gives a diffused band structure as the time required for a molecular
vibration is 10-14s. At transitions to higher vibrational energy levels (above the one in which cross over
occurred) will give normal vibrational electronic spectrum with rotational fine structure as the molecule
spends more time as the extreme ends of the vibrational motion and minimum time near the crossing
points.
 Birge and Sponer method

As the vibrational quantum number increases, Δϵ( ϵv+1- ϵv), the energy difference
between the successive levels decreases. At high ‘v’ values, the vibrational
bands overlap and merge together and will become a continuum. If Δϵ is
plotted against the vibrational quantum number V, we get a curve as shown
below. Birge and Sponer observed that area under the Δϵ versus V graph gives
the disassociation energy directly. This is the Birge and Sponer method.

Terms used in UV/VIS spectroscopy:

Chromophore: system which is responsible for the absorption.

Auxochrome: substituent which leads to shift of the absorption maximum.

Bathochromic effect: red shift (towards longer wavelength) of absorption maximum.

Hypsochromic effect: blue shift (towards shorter wavelength) of an absorption maximum.

Hyperchromic effect: increasing absorption intensity.

Hypochromic effect: decreasing absorption intensity.

Electronic Spectra of Polyatomic molecules
The radiations giving electronic spectra can be classified in to 3 regions
Region Wavelength range
1 Visible 400-700nm
2. Near uv 200-400nm
3. Far or vacuum uv < 200nm

The electronic spectra of polyatomic molecules are highly complex. The vibrational
structure and rotational fine structure of electronic spectra can only be observed in the gaseous
states of molecules. In solution the rotational energy levels are not well defined. Hence the
rotational fine structure is not taken in case of solutions. The vibrational bands in such cases are
broad and not sharp.
Most probable transition involves promotion of an electron form the highest occupied
molecular orbital (HOMO) into the lowest unoccupied molecular orbital (LUMO). All
transitions among these are not allowed. When a transition is forbidden the probability of that
transition is low and correspondingly the intensity of absorption is low.
Electrons in vast majority of molecules belong to 3 classes, σ, π and n (non bonding).
Their relative energies are in the following order.

The relative quantities of energy required for the various transitions follows in the order.
ΔEσ→σ*> ΔEn→σ* > ΔEπ→π* > ΔEn→π*
σ→σ* transitions occurs in saturated compounds fall in the vacuum UV region since they
involve high energy. .n→σ* and π→π* transitions fall in the borderline between near and UV
regions. n→π* transitions require the least quantity of energy and they occur in near UV and
visible regions.
 For organic carbonyl compounds, the electronic transitions involve promotion of the
electrons in n, σ and π orbitals in the G.S to the excited ABMO’s. In other words the transitions
of the type σ→σ*, π→π* and n→π* are allowed. The unsaturated compounds having C=C and
C=O groups (such as aldehydes and ketones) show n→π* and π→π* transitions. For aldehydes
and ketones the more intense band near 180nm is due to π→π* transition and the weaker band
(forbidden by Q.mechanics) near 285nm is due to n→π* transition. Olefinic hydrocarbons show
a π→π* transition at 160-170nm.
Functional groups such as C=C, -N=N- which absorb at wavelengths longer than 180nm, are
called chromophores. Other chromophores are nitro, nitroso, carbonyl, thiocarbonyl, sulphoxide
groups as well as aromatic rings. Molecules such as CH3NH2 and CH3I which do not have a π
orbital, show n→σ* transition.
The intensity of an electronic band is determined by the extent of overlap of the wave functions
in the G.S and E.S. Since there is poor overlap of wave functions of the G.S and E.S in the
n→π* transition and there is considerable overlap in the case of π→π* transition, the former is
less intense than the latter. Also in strongly acidic media, the n→π* band disappears due to the
protonation of lone pair of electrons. In fact the protonation may increase the excitation energy to
such an extent that the n→π* transition may shift far out into the UV region and may not be
observed.

The protonation of a functional group introduces profound changes in the spectra. Thus
the spectra in cases are strongly dependent upon pH. Solvent effects too are useful in identifying
the nature of these transitions. The n→π* transitions are altered by solvent effects in cases where
the lone pair electrons in oxygen or nitrogen containing systems interact with polar solvents. The
changes are; Bathochromic effect, Hypsochromic effect, Hyperchromic effect and Hypochromic
effect.
The term Auxochrome refers to an atom or group of atoms which does not give rise to an
absorption band on its own but, when in conjugation with a chromophore, causes a bathochromic
shift and a hyperchromic effect. For instance >C=C< group is a chromophore in ethylene.When
one of the hydrogens is replaced by a halogen atom, a bathochromic shift and a hyperchromic
effect are observed. This is because the lone pair in the halogen atom conjugates with the alkene
double bond. So here halogen atom is an auxochrome. (Ref Puri & Sharma)
Aromatic Systems- Benezne and its substitution products

The π→π* transitions in benzene and benzene derivates lead to absorption bands in the
range 160-270 nm. Although four transitions are expected in benzene, only three bands can be
observed due to a degenerate state. The band at 250 nm also shows vibrational fine structure. In
disubstituted benzenes, p-substitution causes a red shift of the main absorption bands, whereas o-
or m-substitution does not shift the bands much. Spectra of polycyclic aromatic hydrocarbons
may be used as fingerprints for identification of the compounds. Highest and lowest orbitals are
not degenerate so that four transitions may occur. Upon increasing annulation, the bands shift
towards longer wavelengths. Heteroaromatic compounds show roughly the same effects as their
corresponding hydrocarbons. Spectroscopic effects caused by the heteroatom depend on the
electronic properties and on the orientation of the substituent.

Benezene gives the following absorptions;

204nm and 254 nm in the near uv region

& 184 nm in far uv

The absorption at 184 nm is an allowed one and it is strong. The other two are forbidden
and weak. The benzenoid band at 254nm is characteristic of aromatic and hetero aromatic
compounds. it is called B band. When benzene is substituted with a single functional group
three things can happen;

A The intensity of absorption increases

B Bathochromic (red) shift

C Details of spectrum is lost in the fine structure.

As conjugation increases λmax increases and intensity of the line also increases.

π→π* transition in conjugated systems give K band

n→π* transitions give R band

Woodward has set up certain rules to predict the effect of substituents in the conjugated systems
on λmax. They are called Woodward rules. Consider butadiene, π→π* transitions occur with λ max
=217nm. Any substitute to this has been assigned a positive and negative value which must be
added to basic absorption at 217 nm in order to arrive at the absorption frequency of the
substituted molecule. The increments of certain groups are given below

R(alkyl) 5nm

-OR 6nm

-C1, -Br 5nm

-CH=CH- 30nm

OCOR 0

Electronic Spectra of Conjugated molecules- Free Electron Model

In extensively conjugated systems, the π electrons are delocalized over the entire
skeletal framework. It is found that the absorption bands shift to longer
wavelengths as the extent of conjugation increases. As the conjugation extends
from diene, triene to tetraene, λmax increases to a limit of 550- 600nm (for about 20
double bonds) by which stage the polyenes are strongly yellow in colour. Thus
sufficient conjugation can move λmax to visible region.

As the conjugation increases, the intensity of λ max increases. So the

structure of a compound can be established by comparing its spectrum with that
of a closely related model compound.

The Electronic Spectra of Conjugated molecules can be explained by Free Electron molecular
Orbital theory. According to this theory π electrons are delocalized over the entire carbon
skeleton of the molecule and there is no true C-C single bond or C-C double bond. Hence we can
apply particle in a one- dimensional box approach for explaining the electronic Spectra of
conjugated molecules.

The energy of the particle in a one- dimensional box is given as

2 2
nh
E= 2
8m L

n= 1, 2, 3…..
h - Planks constant
L- Length of the box
m - Mass of the electron

The potential energy of the electron is zero between the walls of the box and the potential energy
rises sharply to infinity at the wall.
The electrons in the π MO are filled according to Pauli’s Principle and Hunds rule. Thus
if N is the number of π orbitals, only N/2 π orbitals are filled in the ground state. The longest
wavelength transition (low energy transition) involves the excitation of π electrons from N/2
HOMO to N/2 +1 LUMO. Hence the frequency of electronic transition is given as

ΔE
υ= =¿- EN/2¿ /h …………………………………………………………………. (1)
h

ΔE = h2/8mL2[(N/2+1)2 - (N/2)2]= h2/8mL2(N+1) ………………………………………… (2)

The wavenumber of the absorbed radiation is given by υ = ΔE/hc

υ = h(N+1)/8mL2c ………………………………………………………………………….. (3)

Let us now estimate the chain length L of the conjugated system (the width of the box).
Let us assume now that the length of the box is not equal to the length of the Carbon chain but
equal to the length of the Carbon chain + one extra bond length on either side of the chain.
Hence L= (No of C-C bonds between N Carbon atoms + 2)a ; where a is the C-C bond
length=139pm
= (N-1 + 2)a = (N+1)a (If there are N Carbon atoms there will be N-1 C-C bonds
between them).
Substituting the value of L in equation (3);

υ = h(N+1)/8mc (N+1)2a2

= h/8mc(N+1)a2

= 148137.6/(N+1) (after substituting the values of constants)

…………………………………………….. (4)

The above equation can be modified by assuming an advanced approach; ie by the use of
sinusoidal form of potential energy with a minimum at the centre of the double bond. Hence eqn
(4) becomes

υ=
153000
N +1 (
1
)
+16000 1− ………………………………………………………(5)
N

For example; In 1,3,5-hexatriene molecule N=6

Substituting the value in (4) we get

υ = 148137.6/(6+1)

= 21,162.5cm-1

Using modified free electron MO theory from eqn (5), we get

υ=
153000
6+1
+16000 1− ( )1
6
= 34495 cm-1

Which is closely in agreement with the experimental value.

Charge - Transfer Spectra

Many inorganic species show charge-transfer absorption and are called charge-transfer
complexes. For a complex to demonstrate charge-transfer behavior one of its components must
have electron donating properties and another component must be able to accept electrons.
Absorption of radiation then involves the transfer of an electron from the donor to an orbital
associated with the acceptor.
Metal complexes with organic ligands show different spectroscopic effects, dependent
upon whether the metalligand bonds are covalent or ionic. If the metalligand bond is essentially
ionic only small changes occur, the spectrum of the complex being similar to that of the
protonated ligand. On the other hand, the spectrum is significantly changed for complexes with
strong covalent metalligand bonds and such complexes are highly colored. Charge-transfer
transitions may occur in the case of covalently bound ligand orbitals and empty or anti-bonding
metal orbitals. Organic ligands forming charge transfer complexes are often used in the analysis
of ions such as Fe, Cu, Cd or Zn.

Absorption Involving d- and f-Electrons

Many transition metal ion solutions are coloured as a result of their incomplete d-levels,
which allows promotion of an electron to an excited state by the absorption of relatively low
energy visible light. The bands are broad & strongly influenced by the chemical environment,
because of the spatial shape & orientation of the d-orbitals. Lanthanides & actinides have
incomplete f-levels & give rise to absorption bands in a similar fashion to transition metals. In
contrast to transition metal ion spectra, those of the lanthanides/actinides contain narrow, well-
defined bands which are little affected by ligands & the local chemical environment.
Photoelectron spectroscopy
The absorption of a photon of high enough energy may cause an electron to be ejected
entirely from a molecule. In photoelectron spectroscopy, molecules are irradiated with high
frequency, monochromatic light and the kinetic energy of the emitted photoelectrons is analyzed.
The resulting photoelectron spectrum provides information on the energy levels of the orbitals
from which the electrons were emitted. Conservation of energy dictates that if the incoming
photon has frequency, v, and the ionization energy for the electron in an orbital is I, the kinetic
energy of the emitted photoelectron is:

1/2mv2 = hυ - I

The kinetic energy of the electrons is determined from the strength of the electric or
magnetic field required to bend their path into a detector. The slower the ejected electron, the
lower in energy the molecular orbital from which it was ejected. Ultraviolet photoelectron
spectroscopy provides information on the energy levels of the molecular orbitals of the valence
electrons of molecules; X-ray photoelectron spectroscopy provides information on the energy
levels of core electrons. If the apparatus has sufficient resolution of photoelectron kinetic
energy, it may be possible to resolve fine structure in the photoelectron spectrum associated with
the vibrational levels of the molecular cation formed by the ionization.