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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.
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
DE = hn = hc/
Wavelength = c/n, Wavenumber, v = nc
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nupper nlower
exp DE
kT
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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
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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Vibrational Transition
<<
2000-4000 cm-1
Thus the various types of energy transitions occur in different regions of the EMR spectrum and do not overlap.
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.
Jablonski diagram
Absorption and emission pathways
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.
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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