XV74

UV-vis (Electronic) Spectra-2014 -Ch.13 Atkins, Ch.19 Engel

Most broadly used analytical tech / especially bio-applic.
inexpensive optics / solvent & cell usually not problem
intense transitions sensitive, low concentrations
broader transitions mix in vibrational excitation / low res.
Optical Spectroscopy Processes diagram

But some molecules dont absorb in UV-region >200nm

all absorb in vac. UV (<200nm) e.g. salts, ions, saturated
molecules: hydrocarbons, sugars, alcohols, etc.
UV - -systems, open shells, broad less detail structure
many do not fluoresce, compete paths for energy transfer

XV75

Basic idea excite electrons to a new state

Thus - new potential surface, i.e. vibrations will differ
Franck-Condon Principle
vertical transitions
Nuclear motion slow compared
to transition time
effectively frozen nuclei
In excited state, molecule first
relaxes to new equilibrium
structure, then fluoresces
Vibrational energy goes to solvent
vibrational relaxation
Mirror image spectra
A absorbance
F fluorescence
broad bands many component
Vibronic transitions:
ge g exe ex
vibronic overlap often
unresolved
Born-Oppenheimer, separate
integrals: elec(r) and nucl(R)
Intensity (A or F) ~ De-g = ex* g d 2
(Dipole strength)
= (exe ex* ge g d 2
=(exe*ge dr2(ex*g dR2
integrated
distribution over vib
intensity
F-C factor-vertical trans

XV76

F-C allowed transitions

Vertical excitation of electrons,
means nuclei stay near minimum of
originating surface. Favor vibrations
at turning point reference to minimum
of other state. Multiple vibrations get
excited but with different frequencies,
relative intensity given by square of
overlap of vibrational functions, initial
and final states F-C envelop

Potential energy surfaces shapes Atkins above, Engel (p.459-60)

Top, left: Vibration Spacing reflect: A excited, F ground state
Bottom: bigger potential shift, more distribution,
eventually get continuum (right, structurelessdissociate)

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Shift of potential surfaces

reflected in F-C bandshape, excitation
to continuum, broad structureless,
dissociating state
Gap - Absorb and Fluor
shift, different geometry
vibs closer, bond strength

Molecule - electronic energies change with nuclear positions,

and gives rise to different
vibrational levels
Ex. Potential energies of I2
electronic statesMany states, not all transitions
seen selection rules
Plus each has own vibration
energies

XV78

Absorbance

A = -log10 I/I0 = b c {b path, c conc.

molecular property relate to dipole strength D

QM link: Intensity - A ~ D10 = 1* 0 d 2
Electronic Spectra Broad - vibrations couple electronic
Spectra reflect: h = E
a) change electronic energies
Eel = E1 E0
b) change of vibration
(note: frequencies differ)
Evib = (e+)he (g+)hg
initial state typically g = 0
but small g or high T hot band
absorb from g 0
most probable vertical transition
(Franck-Condon)
Fluorescence if relax to e = 0 then can emit photon
Can be mirror image of Absorption, but fluorescence
Vibrational progression reflects lower state
Intensity - IF ~ D01 same probability as absorbance
vibronic pattern differ spacing g
linear: measure IF ~ Iexcite (if excite by absorption)
but measure fluor. signal against null background
extremely sensitive / can even do single molecule
[Problem other relaxation limit quantum yield]

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Ex. absorption/fluorescence spectra vertical surface

Selection rules
less simple than for rotations and vibrations
a. Molecule must change dipole moment, normally
change electronic states where charge is dislocated
(if center of symmetry gu allowed, polyatomic use symmetry)
b. Spin not affected by E-field (light) S = 0
c. Between states, vibrations change - v = 0, 1, 2, . .
But rotations restricted: J = 0, 1

XV80

What kind of molecules have measurable Absorbance?

a. All absorb vacuum UV ( < 200 nm , > 50,000 cm-1)
everything eventually (shorter ) absorbs
Closed shell, saturated, light atoms only at higher (vacUV)
e.g.:
H2O , MeOH
-- closed shells, saturated
CnH2n+2 , CnH2n-m Fm+2
-- light atoms
LiF , CaF2
-- salts
He, Ne, Ar
rare gas
b. UV (ultraviolet) (: 200-400 nm, = 50-25,000 cm-1)
big contribution are -systems
aromatics, polyenes, conjugated
O
O

hetero atom:

+ lone pair delocalize

plus heavier atom systems

S S

C I

(also Cl-, Br - . . .)

c. in Visible (: 400-700 nm , = 25,000-14,000 cm-1)

need very delocalized system (-electron)
N
N +

N
N

retinal
(off a bit)

dyes are like this-aromatic

porphyrin

or open shells radicals

transition metal Fe(CN)6-3 , CuII(SH)2(NH3)2 etc.
complexes :
red
blue
d. near-IR (: 700-2500 nm , = 14,000-4,000 cm-1)
mostly transition metals (d-d), open shells, NO, 1O2
N O

XV81

Benzene electronic spectra * -displaced surfaces

vibronic progressions, vi = 1, 2, totally sym. modes,
for first trans. forbidden, build on four asym modes vj = 1
allowed transition A1gE1u at <200nm (intense, ~105),
Triplet trans. at ~330 nm, S=1 forbidden (very weak, ~10-3)

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XV83

Comparison of porphyrin and hemoglobin absorb. with O2 & CO

Rhodopsin visible
absorbance in
dark and changes
after exposure
and adding
11-cis-retinal

XV84

Transition metal complexes open shells, visible absorb

dd transitions are weak because l ~ 0

Mn+2 - d5, ground state - 6A1g (6S related)

absorbance very weak, S0