Vibronic interaction

I, B. Bersuker, The Jahn-Teller effect and Vibronic Interactions in Modern Chemistry, Plenum Press, New York, 1984. 

I, B, Bersuker and V. Z, Polinger, Vibronic Interactions in Molecules and Crystals, Springer-Verlag, New York, 1989. 

Now, we examine the effect of vibronic interactions on the two adiabatic potential energy surfaces of nonlinear molecules that belong to a degenerate electronic state, so-called static Jahn-Teller effect. 

We now take vibronic interactions into account. In this case, we must determine vibronic states rather than the electronic and vibrational ones. For example, if X3 in a degenerate E vibration is singly excited in an E electronic state, we obtain the vibronic states A 0 0 since "E 0 =... 

R, Englman, The Jahn-Teller Effect in Molecules and Crystals, John Wiley. Sons, Inc., Interscience, New York, 1972 I, B. Bersucker and V. Z. Polinger, Vibronic Interactions in Molecules and Crystab, Springer Verlag, 1989. 

I.B. Bersuker, V.Z. Polynger, Vibronic interactions in molecules and crystals, Nauka, Moscow, 1983 (in Russian). 

Techniques other than UV-visible spectroscopy have been used in matrix-isolation studies of Ag see, for example, some early ESR studies by Kasai and McLeod 56). The fluorescence spectra of Ag atoms isolated in noble-gas matrices have been recorded (76,147), and found to show large Stokes shifts when optically excited via a Si j — atomic transition which is threefold split in the matrix by spin-orbit and vibronic interactions. The large Stokes shifts may be explained in terms of an excited state silver atom-matrix cage complex in this... 

Blauer G (1974) Optical Activity of Conjugated Proteins. 18 69-129 Bleijenberg KC (1980) Luminescence Properties of Uranate Centres in Solids. 42 97-128 Boca R, Breza M, Pelikan P (1989) Vibronic Interactions in the Stereochemistry of Metal Complexes 71 57-97... 

Azulene (XI) possesses a transannular bond which has the same effect as those of bowtiene (Fig. 3). The splittings of the top filled and bottom empty degenerate orbitals of cyclododecapentaene in this case are half the corresponding splitting in the case of bowtiene, and are not large enough to produce an effective vibronic interaction between the ground and lowest excited states of the resultant azulene molecule. 

Bersuker IB (1984) The jahn-teller effect and vibronic interactions in modern chemistry. Plenum Press, New York... 

We now take vibronic interactions into account. In this case, we must determine vibronic states rather than the electronic and vibrational ones. For example, if X3 in a degenerate E vibration is singly excited in an E electronic state, we obtain the vibronic states evA evA 2 evE, since VE eE = evA evA 2 evE . If the same vibration is doubly excited (e.g., if v 2 = 2, with the symmetric product being [vE v E = VA VE Note that the associated antisymmetric product is M ), we get the vibronic species ( Aj VE ) eE = evA evA 2 2evE. Table XIII shows the symmetries of the lowest 25 vibrational and vibronic states. In turn, the lowest 26 levels calculated for Li3... 

Sumi H (1998) V-I characteristics of STM processes as a probe detecting vibronic interactions at a redox state in large molecular adsorbates such as metalloproteins. J Phys Chem B 102 1833-1844... 

In principle, refined and relatively reliable quantum-theoretical methods are available for the calculation of the energy change associated with the process of equation 2. They take into account the changes in geometry, in electron distribution and in electron correlation which accompany the transition M(1 fio) — M+ (2 P/-), and also vibronic interactions between the radical cation states. Such sophisticated treatments yield not only reliable predictions for the different ionization energies 7 , 77 or 7 , but also rather precise Franck-Condon envelopes for the individual bands in the PE spectrum. However, the computational expenditure of these methods still limits their application to smaller molecules. We shall mention them later in connection with examples where such treatments are required. 

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