Electronic state affecting factors

These selection rules are affected by molecular vibrations, since vibrations distort the symmetry of a molecule in both electronic states. Therefore, an otherwise forbidden transition may be (weakly) allowed. An example is found in the lowest singlet-singlet absorption in benzene at 260 nm. Finally, the Franck-Condon principle restricts the nature of allowed transitions. A large number of calculated Franck-Condon factors are now available for diatomic molecules. 

However, the extent of the activity enhancement cannot be related to the higher surface area of this material. Two possible explanations were proposed to account for the effect of mirror plane composition on combustion activity one is related to the different oxidation state of the cation in the mirror plane the other is associated with the crystal structure of layered-alumina materials (i.e., magne-toplumbite and (3-Al203) which have different population and co-ordination of the ions in the mirror planes. Both these electronic and structural factors can, in principle, affect the redox properties. 

Only a few examples of these planar tetrahedral equilibria have been successfully investigated and there remain unanswered questions about the dynamics. Nevertheless, it seems reasonable to regard these equilibria as intramolecular isomerizations in which the spin state change is not an important factor in the dynamics. Electron spin affects the bonding, geometry, and thermodynamics of the two isomers, but there is apparently sufficient mixing of the singlet and triplet states to allow their interconversion to be adiabatic. 

Another factor that can affect the width of the spectrum is the difference between the vibrational frequencies in the excited and ground electronic states. The trends in the spectral changes can be readily explained from the time-dependent... 

Consider first some of the factors affecting the design of such laser schemes. Ground electronic state based laser enhancement schemes [216, 3 366] rely on the induction of nuclear dipole moments to aid in promoting a desii reaction [30, 367], For example, the use of infrared (IR) radiation has been propoS to overcome reaction barriers on the ground electronic state [30, 367]. However proposal requires powers on the order of terawatts per centimeter sipis (TW/cm2). At these powers nonresonant multiphoton absorption, which irtvar leads to ionization and/or dissociation, becomes dominant, drastically reducin, yield of the reaction of interest. 

So far, this discussion of selection rules has considered only the electronic component of the transition. For molecular species, vibrational and rotational structure is possible in the spectrum, although for complex molecules, especially in condensed phases where collisional line broadening is important, the rotational lines, and sometimes the vibrational bands, may be too close to be resolved. Where the structure exists, however, certain transitions may be allowed or forbidden by vibrational or rotational selection rules. Such rules once again use the Born-Oppenheimer approximation, and assume that the wavefunctions for the individual modes may be separated. Quite apart from the symmetry-related selection rules, there is one further very important factor that determines the intensity of individual vibrational bands in electronic transitions, and that is the geometries of the two electronic states concerned. Relative intensities of different vibrational components of an electronic transition are of importance in connection with both absorption and emission processes. The populations of the vibrational levels obviously affect the relative intensities. In addition, electronic transitions between given vibrational levels in upper and lower states have a specific probability, determined in part... 

Exchange experiments arc also the basis of our estimate of the relative importance of the two steps differences in rate of hydrolysis of acyl derivatives depend chiefly on how fast intermediates are formed, and also on what fraction of the intermediate goes on to product. As we have said, the rate of formation of the intermediate is affected by both electronic and steric factors in the transition state, a negative charge is developing and carbon is changing from trigonal tow ard tetrahedral. 

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