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CHEM F111 General Chemistry Lecture 28

Molecular Spectroscopy - Electronic
01-November-2013 1
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Electromagnetic Radiations
Depending on how the electrons are moved to create the light for each beamline, different colors of light can be produced.

Only this small range is visible to the human eye

Different experiments use different colors, or wavelengths, of light

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Internal Energy of Molecules

Absorbance
E2 E2

Emission
DE = hn

D E = hn
E2 E1

Absorption: A transition from a lower level to a higher level with transfer of energy from the radiation field to an absorber, atom, molecule, or solid. Emission: A transition from a higher level to a lower level with transfer of energy from the emitter to the radiation field. The 2 types of transitions are: Radiative - photon is absorbed/emitted

Nonradiative - energy transferred between molecule to the surroundings

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Internal Energy of Molecules

Etotal = Etrans + Eelec + Evib + Erot + Enucl
Eelec: electronic transitions (UV, X-ray) Evib: vibrational transitions (Infrared) Erot: rotational transitions (Microwave) Enucl: nucleus spin (nuclear magnetic resonance) or (MRI: magnetic resonance imaging)

DE = hn = hc/
Wavelength = c/n, Wavenumber, v = nc
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Population of Energy Levels

At any finite T, molecules will be distributed among available E levels due to thermal agitation The exact distribution among energy levels will depend upon the temperature and separation between energy levels according to Boltzmann statistics

nupper nlower

exp DE

kT
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k = 1.38 10-23 JK-1 (Boltzmanns constant) DE = separation in energy level

Population of Energy Levels

Population of energy levels Net absorption depends on the difference between the populations of the energy levels; more populated the ground state, the more intense the net absorption is. Two factors that influence absorption are the energy level spacing and the temperature.
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Electronic Spectroscopy

Ultraviolet (UV) and visible (VIS) spectroscopy This is the earliest method of molecular spectroscopy. A phenomenon of interaction of molecules with ultraviolet and visible lights. s* Unoccupied levels Absorption of photon results in p* electronic transition of a molecule, and electrons are Atomic orbital promoted from ground state to E n higher electronic states usually Occupied levels from a molecular orbital called p HOMO to LUMO.
s
Molecular orbitals

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Electronic transition
Can be assigned to different transition types according to the molecular orbital involved, such as -> * (in alkenes or benzene), n ->* (in keto group). Due to their symmetry property in MOs, such transition can be allowed (high intensity) or forbidden (low intensity). Absorptions with high are allowed transitions, and low absorptions are forbidden transition.

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Molecular Energy Levels

Excited Electronic State
Relative energy of the spacings between different energy levels Rotational Transition

<<

Vibrational Transition

<<

Electronic Transition 10000-50000 cm-1

Rotational 1-20 cm-1 Energy Levels

2000-4000 cm-1

Vibrational Energy Levels

Thus the various types of energy transitions occur in different regions of the EMR spectrum and do not overlap.

Ground Electronic State

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Molecular Energy Levels

Radiation can be absorbed or emitted if the molecule changes any of its energy states
Excited Electronic State

Rotational Energy Levels

Vibrational Energy Levels

Ground Electronic State

Rotational Transition Microwave

Vibrational Transition Infrared

Electronic Transition UV-Visible

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Frank-Condon Principle
The nuclear motion (10-13 s) is much slower as compared with electronic motion in transition (10-16 s), so it is negligible during the time required for an electronic excitation.

Since the nucleus does not move during the excitation, the internuclear distance keeps the same, and the most probable component of a electronic transition involves only the vertical transitions where
the position and momentum of the nuclei dont change.

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Molecular Energy Levels

The excitation going from = 0 (GS) to = 3 (ES) is the most probable one for vertical transition because it falls on the highest point in the electron probability curve for = 3 in ES.

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Jablonski diagram
Absorption and emission pathways

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Selection Rules
For an electron to transition, certain quantum mechanical constraints apply these are called selection rules. Thus all transitions that are possible are not observed. Gross Selection Rules: Specifies the general features a molecule must have if it is to have a spectrum of a given kind. e.g. a vibration is ctive only if there is a change in dipole moment. Specific Selection Rules: A detailed study of the transition moment leads to the specific selection rules that express the allowed transitions in terms of the changes in quantum numbers.

Selection rules of electronic transition

Spin selection rule: there should be no change in spin orientation or no spin inversion during these transitions. Thus, SS, TT, are allowed, but ST, TS, are forbidden. (S = 0 transition allowed). Angular momentum rule: the change in angular momentum should be within one unit (0 or 1).
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