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University of Cambridge
Vibrational transitions occur providing the electronic transition dipole moment and the
Franck-Condon factors are non-zero. In the infrared, the selection rules for v arise from
the symmetry of the different vibrational wavefunctions, and are strictly Δv = ±1 for the
simple harmonic oscillator. For an anharmonic oscillator, this strict rule begins to break
down and overtones are allowed, albeit with rapidly declining intensity. For vibrational
transitions between different electronic levels, this rule breaks down completely and
there is now no longer any restriction on Δv, so that every v’ ← v” transition has some
probability, giving rise to many spectral lines. However, absorption spectra from the
ground state are much simpler: virtually all the molecules are in their lowest vibrational
state (v” = 0), so that the only transitions we observe are (0, 1), (0, 2), (0, 3) etc.
Note that the upper state is given first within the brackets. Each set of transitions in a
band is called a v’ progression, since the value of v’ increases by unity for each line in
the set. The lines in a band are closer together at high frequencies because of the
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anharmonicity of the upper state vibrations, which causes vibration energy levels to
converge. Note that, in general, the spacings of vibrational energy levels in the two
electronic states are different.
To quantify:
Δεtotal = Δεelec + Δεvib. = (ε’ – ε”) +
+ [(v’ + 1/2)ϖe’ – xe’(v’ + 1/2)2 ϖe’ – (v” + 1/2)ϖe” – xe”(v” + 1/2)2 ϖe”]
cm-1
If a sufficient number (at least five) lines can be resolved in the band, the values of xe’,
ϖe’, xe”, ϖe” and (ε’ – ε”) can be calculated. Information on the excited electronic states is
particularly valuable, since such states are extremely unstable, and therefore short-lived.
v” = 0 v” = 1 – 0 1 v” = 2 – 1 2 v” = 3 – 2 3
v’ = 0 64748 2143 62605 2117 60488 2090 58398
v’ = 1 – 0 1480 1480 1480 1480
1 66228 2143 64085 2117 61968 2090 59878
v’ = 2 – 1 1440 1440 1440 1440
2 67668 2143 65525 2116 63409 2090 61319
v’ = 3 – 2 1402 1402 1402 1402
3 69070 2143 66927 2117 64810 2090 62720
(1) If the internuclear distances in the upper and lower states are equal (re” ≈ r e’), the
most probable transition is (0, 0), as indicated by the vertical line in the figure below.
However, there is a non-zero probability of (1, 0), (2, 0), (3, 0) etc. transitions. The
successive lines will therefore have rapidly diminishing intensities.
(2) If the excited electronic state has a slightly larger nuclear separation than the ground
state (re” > re’), the most probable (and thus most intense) transition is (2, 0). The
intensities of the neighbouring transitions are lower.
(3) When the excited electronic state has a considerably larger nuclear separation than
the ground state (re” >> re’), the vibrational state to which the transition takes place
has a high v’ value. Further, transitions can occur to levels where the molecule has
energy in excess of its dissociation energy. From such states the molecule will
dissociate without any vibrations and, since the fragments which are formed may
take up any value of kinetic energy, the transitions are not quantized and a
continuum results.
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cause no more than dissociation. The dissociation products separate with zero kinetic
energy, and we have:
v˜ continuum limit = Do” + Eex cm-1
When the internuclear distances in both states are such that transitions near to the
dissociation limit are of negligible probability, no continua appear in the spectra.
However, it is still possible to determine the dissociation energy by noting how the
vibrational lines converge. The separation between the neighbouring vibrational levels:
Δε = εv+1 – εv = ϖe[1 – 2xe(v + 1)] cm-1
This separation decreases with increasing v, and the dissociation limit is reached when
Δε tends to zero. The maximum value of v is vmax, where
ϖe[1 – 2xe(vmax + 1)] = 0
so that
vmax = (1/2xe) – 1
Since xe is of the order of 10-2, vmax is about 50.
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To summarize, provided that transitions are assigned correctly, the two methods
available for the determination of the dissociation energies Do” and Do’ are:
(1) The Birge-Sponer extrapolation
(2) If the Morse potential is assumed to be correct, the equilibrium vibration
frequencies νe’ and ν e” and the anharmonicity constants v˜ exe’ and v˜ exe” can be
determined for the two levels using:
v˜ (v” = 1 ← v” = 0) = v˜ e” – 2 v˜ exe”
€ €
v˜ (v” = 2 ← v” = 1) = v˜ e” – 4 v˜ exe”
v˜e2 €
€ De = €
4 v˜e x e €
€ €
A minimum of five entries in the Deslandres table (the bordered region) is required for
the determination of the dissociation energies of both electronic states.
€
Rotational fine structure of electronic-vibrational transitions
If we ignore centrifugal distortion and use the Born-Oppenheimer approximation, the
total energy of a diatomic molecule is:
˜ J(J + 1)
εtotal = εelec + εvib + B cm-1
while changes in the total energy are
€
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where J’ = 0, 1, 2,…
(2) R branch: ΔJ = +1, J’ = J” + 1
€ € € € € €
ν˜ R = v˜v',v" + ( B˜ ’ + B˜ ”)(J” + 1) + ( B˜ ’ – B˜ ”) (J’ + 1)2 cm-1
where J” = 0, 1, 2,…
These two equations can be combined into:
€ € € € €
€ ν˜ P,R = v˜v',v" + ( B˜ ’ + B˜ ”) m + ( B˜ ’ – B˜ ”) m2 cm-1
where m = ±1, ±2,… with positive m values for the R branch (ΔJ = +1) and negative
values for the P branch (ΔJ = –1). Note that m cannot be zero (as this would correspond
€ € € € € €
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to J’ = –1 for the P branch), so that no line from the P and R branches appears at the
band origin, v˜v',v" . The figure shows the resulting spectra for ˜’< B
B ˜ ” and a 10%
˜ ’ and
difference in the magnitude of B ˜ ”.
B P branch lines appear at the low
wavenumber side of the band origin, and the spacing between the lines increases with
€ €
m. €
The R branch appears on the high wavenumber side, and the line spacing decreases
€ at which
rapidly with m. The point € the R branch separation decreases to zero is known
as the band head.
The
€ Fortrat € €
€ diagram € €
Rewrite the expressions for the P, R and Q lines with continuously variable parameters p
and q:
ν˜ P,R = v˜v',v" + ( B˜ ’ + B˜ ”) p + ( B˜ ’ – B˜ ”) p2
ν˜ Q = v˜v',v" + ( B˜ ’ – B˜ ”) q + ( B˜ ’ – B˜ ”) q2
Each equation represents a Fortrat parabola, where p takes both positive and negative
€ € € € € €
values, while q is always positive. The band head is clearly at the vertex of the P, R
parabola. € € the position
€ € We calculate € € of the vertex by differentiation:
˜’+ B
d ν˜ P,R /dp = B ˜ ” + (B
˜’– B
˜ ”) p = 0
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or
˜’+ B
p = – (B ˜ ”)/2( B
˜’– B
˜ ”) for band head
˜’< B
If B ˜ ”, the band head occurs at positive p values (i.e. in the R branch). Conversely,
˜’> B
if B ˜ ”, the band head is found at negative p values (i.e. in the P branch). A 10%
€ € € €
˜ ’ and B
difference between B ˜ ” gives p = 11.
€ €
€ €
€ €
Predissociation
A phenomenon called predissociation arises when the Morse curves of a molecule in
two different excited states intersect, with one of the states being stable (with a
minimum on the energy curve), and the other continuous. Suppose a transition takes
place from some lower state into the vibrational levels shown bracketed on the left.
Now if a transition takes place into the levels labelled a, b or c, a normal vibrational-
electronic spectrum occurs, complete with rotational fine structure. Two such bands
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appear on the left of the spectrum below. However, for a transition into the levels
labelled d, e or f, the molecule may “cross over” onto the continuous curve and
dissociate. Such transition (known as “radiationless transfer”) is faster than the time
taken by the molecule to rotate (ca. 10-10 s), but usually slower than the vibrational time
(ca. 10-13 s). Thus predissociation will occur before the molecule rotates (destroying the
rotational fine structure), while the vibrational structure is preserved. If the cross-over
is faster than the vibrational time, a complete continuum will be observed.
The energies of the two s orbitals depend on the internuclear distance as shown below.
Using the same procedure we obtain the two 2pσ orbitals by combining atomic 2p z
orbitals:
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The figure below shows the various orbitals in order of increasing energy. For light
diatomic molecules, such as Li2, there is considerable overlap and interaction between
2pπu, 2pσg, and 2sσu* orbitals. For H2 this overlap does not occur, so that the two cases
are considered separately.
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€ €
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The same argument applies to spin angular momentum, with the projection of spin
angular momentum along the inter-nuclear axis denoted Σ (equivalent to S in an atom).
This Σ is not to be confused with a Σ state, for which Λ = 0. Thus for a diatomic
molecule, the total angular momentum J (neglecting nuclear spin) is now the vector sum
of the orbital (Λ), spin (Σ) and rotational (R) angular momentum:
Note that the rotational angular momentum is perpendicular to the inter-nuclear axis
(since Iz = 0). The total angular momentum thus has a projection Ω (in units of h) along
the inter-nuclear axis. There are always 2S+1 spin components, where 2S+1 is the spin
multiplicity.
Each electronic state can thus be described by a term symbol of the form:
(spin multiplicity)
[Component of L](net angular momentum component)
2S+1
or ΛΩ
NO, which in its ground state has an electronic configuration …(2pσ)2(2pπ)4(2pπ∗), has a
single unpaired electron. Its spin multiplicity is thus 2 (a doublet state), and it has total
orbital angular momentum of 1 (an unpaired π electron). Its term symbol is thus 2Π, or
more completely 2Π1/2 or 2Π3/2, depending on whether the spin and orbital angular
momentum components are parallel or anti-parallel. Clearly NO may also possess
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rotational angular momentum, but this does not affect the term symbol which refers to
the electrons alone.
Two additional subscripts and superscripts are used in term symbols. The parity
indicates whether a wavefunction has the same sign (g) or the opposite sign (u) under
the process of inversion. Heteronuclear molecules do not have centres of inversion and
thus g and u are not applicable. The second parameter indicates the symmetry of the
electronic wavefunction with respect to reflection in a plane containing the nuclei, and
is applied only to Σ wavefunctions. If an electronic orbital wavefunction is symmetric
with respect to reflection (Σ+) it must, by the Pauli principle, be associated with an anti-
symmetric electron spin wavefunction, and vice-versa.
For example, the ground state electronic configuration of O2 is …(2pσ g)2(2pπu)4(2pπ∗g)2.
Hund’s rules indicate that the lowest energy state is the triplet (which is symmetric in
−
spin), and the term symbol is thus 3 Σ g .
(1sσg2pσg). We have again a 1Σ state, since both electrons are σ, but the overall state is
now odd (a combination of an electron arising from an even 1s state with an electron
from an odd p state gives and overall odd state). Thus (1sσg2pσg) 1Σu+.
(1sσg2pπu). Now Λ = λ1 + λ2 = 1, since one electron is in a π state and one originates from
a 2p orbital, the overall state is (1sσg2pπu) 1Πu.
The energies of the three states are 1Σu+ < 1Πu < 1Σg+.
Similar states are obtained by excitation to 3s and 3p states, 4s and 4p states, etc. In
addition, for n = 3, 4,… electrons can also be excited to the nd orbital. In this case we
have for the energies: (1sσndδ) 1Σg+ < (1sσndπ) 1Πg < (1sσndδ) 1Δg.
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Transitions between the various energy levels follow the selection rules:
1. ΔΛ = 0, ±1
This is rationalised in terms of conservation of angular momentum of molecule plus
photon which has a spin angular momentum of h. For ΔΛ = 0, rotational angular
momentum changes by one (ΔJ = ± 1). Thus transitions Σ ↔ Σ, Σ ↔ Π and Π ↔ Π,
etc. are allowed, but Σ ↔ Δ, for example, is not allowed.
2. ΔS = 0.
Transitions which change the multiplicity are weak for molecules formed of light atoms,
where spin-orbit coupling is small. For heavier atoms, spin-orbit coupling effects are
larger, and transitions for which ΔS ≠ 0 can be seen.
3. ΔΩ = 0, ±1.
Σ+ states can go only to into other Σ+ states (or to Π states), while Σ– can go only to Σ– (or
Π). Thus Σ+ ↔ Σ+ and Σ– ↔ Σ–
g ↔ u (where applicable).
Consider now some triplet states of molecular hydrogen (S = 1). Both electrons occupy
the same orbital, so that the state of the lowest energy will be either (1sσ g2sσg),
(1sσg2pσg) or (1sσ g2pπu). The first two are 3Σ states, and the third is 3Π. Following the
above selection rules, the order of the energies will be:
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The O2 molecule
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The only allowed electronic electric dipole transition from the ground state is B ← X.
As O2 is homonuclear, no vibration-rotation spectrum would be expected within the X
state. Thus O2 would not be expected to absorb at wavelengths longer than ~ 200 nm.
Given the shapes of the two potential energy curves, this absorption would be expected
to be very temperature dependent (stronger at higher temperatures).
Hückel molecular orbital theory has been used to obtain a semi-quantitative picture of
the π-electronic structure of a number of organic molecules. Radiative transitions may
occur between these different electronic states.
The non-bonding state, n, corresponds to the lone pairs of electrons on the oxygen atom.
In its electronic ground state the HOMO (the X state) is the n-state. Promotion of
electrons leads to A and a states etc. The lowest energy electron promotion is to the π*
state, leading to a π* ← n transition, which occurs at ~290 nm. The other transitions
shown occur at shorter wavelengths (higher energies), e.g. the σ* ← n occurs at 190 nm.
now two non-bonding p orbitals, N 1 and N 2, and two bonding orbitals formed by
overlap between sp hybrids and hydrogen 1s, called b1 and b2. Given that the energy of
a non-bonding orbital is higher than that of a bonding orbital and that the sp orbital is
lower in energy than a p bonding orbital, we plot the energy changes for a smooth
transition from 90o to 180o bonding.
We see that (1) the energy of N1 remains constant; (2) the energy of the bonding orbital
a1 decreases as it passes over into the stronger b1 orbital; (3) bonding orbital a2 becomes
non-bonding N2, thus increasing in energy; (4) bonding orbitals b1 and b2 are formed by
absorption of the non-bonding s into a1; (5) 90o to 180o represent maxima and minima on
the energy curves.
Consider BeH2. Be has the electronic ground state configuration 1s22s2, with two outer
bonding electrons. Each hydrogen atom contributes a further electron, so that BeH2 has
four electrons to place into molecular orbitals. The most stable state will be for two
electrons to go into b1 and two into b 2, thus producing a linear molecule. However,
when the molecule is electronically excited, the next available orbitals for the excited
electron are N 2 or N1. With a configuration b12b21N21 the most stable state will be at a
bond angle α. Thus the excited state is bent.
Linear molecules such as CO2 and HC ≡ CH become bent on excitation.
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The effect is that the LUMO π* orbital is shifted downwards, and the π* ← n absorption
shifts to lower energy. Repeated conjugation increases this effect. When sufficient
conjugation is present, the energy of the LUMO π* orbital is lowered to the point where
ν2 corresponds to the visible region of the spectrum (~500 nm rather than 290 nm), a
feature which is exploited in tuneable dye lasers.
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An important example is the photochemical mechanism of vision. The retina of the eye
contains “visual purple”, a combination of a protein with 11-cis-retinal, which acts as a
chromophore and is a receptor of photons entering the eye. 11-cis-retinal itself absorbs
at 380 nm, but in combination with the protein the absorption maximum shifts to ca. 500
nm and tails into the blue. The conjugated double bonds are responsible for the ability
of the molecule to absorb over the entire visible region. They play another important
role: in its electronically excited state the conjugated chain can isomerize by twisting
about an excited C=C bond, forming 11-trans-retinal. The primary step in vision is
photon absorption followed by isomerization, which triggers a nerve impulse to the
brain.
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Phosphorescence. The initial radiation takes the molecule into an excited electronic
state. Because the energy curves of the singlet and triplet state cross one another, the
molecule may undergo intersystem crossing and become a triplet state. This happens
when the molecule contains a heavier atom, such as S, because the spin-orbit coupling is
then large. The molecule deposits its energy via collisions with the surrounding
molecules, but becomes trapped at the lowest vibrational energy level of the triplet. It
cannot radiate its energy, because return to the ground state is spin-forbidden.
However, the radiative transition is not totally spin-forbidden because of the spin-orbit
coupling, so that the molecule is able to radiate weakly.
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