Electronic excited states spectrum intensities

Resonance Raman spectroscopy has been applied to studies of polyenes for the following reasons. The Raman spectrum of a sample can be obtained even at a dilute concentration by the enhancement of scattering intensity, when the excitation laser wavelength is within an electronic absorption band of the sample. Raman spectra can give information about the location of dipole forbidden transitions, vibronic activity and structures of electronically excited states. A brief summary of vibronic theory of resonance Raman scattering is described here. 

Comparison of the UV spectrum of polystyrene in the 2600 A region with that of toluene shows a close relationship in terms of both extinction coefficients and vibronic fine structure. The effect of para substituents is most conveniently characterized by the shift in the band corresponding to the a0-o transition. The comparison of substituent effects on the electronic excited states of thepara substituted polystyrenes parallels those for the corresponding para substituted toluenes. Such a correlation would only be expected if the tr - n transitions were effectively localized within a given pendant group of the polymer system. This conclusion is reinforced by the observation that polystyrene and toluene show similar shake up structure in their ESC A spectra with respect to both band profiles and intensities (when due... 

A variety of spectroscopic methods has been used to determine the nature of the MLCT excited state in the /ac-XRe(CO)3L system. Time-resolved resonance Raman measurements of /ac-XRe(CO)3(bpy) (X = Cl or Br) have provided clear support for the Re -a- n (bpy) assignment of the lowest energy excited state [44], Intense excited-state Raman lines have been observed that are associated with the radical anion of bpy, and the amount of charge transferred from Re to bpy in the lowest energy excited state has been estimated to be 0.84 [45], Fast time-resolved infrared spectroscopy has been used to obtain the vibrational spectrum of the electronically excited states of/ac-ClRe(CO)3(bpy) and the closely related/ac-XRe(CO)3 (4,4 -bpy)2 (X = Cl or Br) complexes. In each... 

The spectrum of radiation from electronically excited states of atoms appears as lines, when the emission from a hot gas is diffracted and photographed, whereas radiation from these excited states of molecules appears as bands because of emission from different vibrational and rotational energy levels in the electronically excited state. Equation (26) shows that the intensity of radiation from a line or band depends upon the temperature and concentration of the excited state and the transition probability (the rate at which the excited state will go to the lower state). Since the temperature term appears in the exponential, as the temperature rises the exponential term approaches unity, as does the ratio of the concentration of the excited (emitting) state to the ground state (as T approaches oo, Ng = Nj). The concentrations of both the ground and excited states, however, reach a maximum, and then decrease due to the formation of other species. The line or band intensity must also reach a maximum and then decrease as a function of temperature. This relationship can be used to determine the temperature of a system. 

In this method, two pulsed lasers are used, both usually in the nanosecond regime. One (the burn laser) is operated at high power, and is scanned across the absorption spectrum. It excites molecules (or clusters) from the particular vibrational level (usually the i = 0 level) to an electronically excited state. The upper state relaxes (radiatively or otherwise) back to the ground state, but not necessarily to i = 0. Thus, depletion in the population of this species is achieved. A second, low-power laser (the probe laser) is fired after a suitable time delay (to allow complete decay of the emission induced by the pump laser). It is tuned to one of the excitation spectrum vibronic bands of the system, and the fluorescence induced by it (the signal ) is continuously monitored. Whenever the frequency of the bum laser corresponds to excitation of the species giving rise to the absorption of the probe laser, the signal is reduced. This reduction appears as a hole that is burned in the spectrum—hence the name of the method. If a different species is excited (another molecule or a different vibrational level) no change in fluorescence intensity is incurred. 

Formally, one can think of the Raman transition probability being proportional to the elements of the polarizability tensor of a bound electron as the exciting frequency approaches the resonance frequency, these elements are enhanced in a Lorentz model of the bound electron. A common example of this mechanism is furnished by the ring-breathing (in-plane expansion) modes of porphyrins. Another mechanism, called vibronic enhancement, involves vibrations which couple two electronic excited states. In both mechanisms, the enhancement factors are nearly proportional to the intensities in the absorption spectrum of the adsorbate. 

A plot of the relative intensity of emitted light as a function of the emission wavelength at a fixed excitation wavelength is termed fluorescence emission spectrum. The fluorescence emission is characterized by the transition from the lowest vibrational mode of the electronically excited state (Si) to the ground state. Therefore, the shape of the emission spectrum is always the same and is independent of the wavelength of the exciting radiation. 

Fig. 10 Theoretically simulated thermally broadened absorption spectrum of [TrpGly Ags] at 300 K compared with the experimental photofragmentation spectrum (solid curve). The black and grey lines correspond to the statistical ensembles of spectra around the most stable isomers I [Fig. 10(b)] and II (Ags additionally bound to the N-terminus), respectively, (b) Thermal ensemble of structures at 300 K obtained from constant-temperature molecular-dynamics simulations, (c) The analysis of the leading excitations between occupied and virtual Kohn-Sham orbitals participating in the intense transition at 288 tun. (d) Electron density difference between the electronically excited state and the ground state of the dominant optically allowed transition at 288 nm. Reprinted with permission from ref. 57. Copyright 2008 by the American Physical Society.

Expressions such as Eq. (11) or (12) are very useful in the discussion of the relative band intensities of the Raman spectra. The values of A Qk that appear in the numerator completely determine the intensity pattern of the spectrum and are the origin of the high selectivity for few normal vibrations. AQk represents the variation of the equilibrium position of the normal mode Qk in going from the ground to the electronic excited state. According to Eq. (12), if the exact path of nuclear equilibrium structure variation from the ground to the excited slate... 

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