By Ilya Prigogine
A part of a sequence dedicated to supporting the reader receive common information regarding a wide selection of themes in chemical physics. Its objective is to give accomplished analyses of matters of curiosity and to motivate the expression of person issues of view.
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Extra resources for Advances in Chemical Physics, Vol. 68
D ) has to be considered. 7) and J,d,, Ja9, and J,da are Coulomb repulsion integrals; represents the repulsion between two charge densities due to one electron in the orbital d and the other in orbital 93. Jd, (JBa) is the timeaveraged repulsion of two electrons in orbital d (%). %’), and Id%),given by Eqs. 5) are self-explanatory: The energy of Id’)or l93’) is twice the one-electron energy plus the time-averaged repulsion of two electrons in one orbital. The energy of Id% ) is the sum of one-electron energies for orbitals d and % plus the electron repulsion integral due to one electron in d and one in 93.
2) due to first and second electron. Then, the matrix for four configurations (without spin consideration) takes the following form: 54 E. LIPPERT ET AL. the first two configurations are already spin adapted, and the linear combinations of the latter two (d9 B d ) / f i leads to singlet and triplet wavefunctions ( i . 3 1, & % )) for plus and minus sign, respectively. Since we treat d’and 9 equally, it is reasonable to consider their linear combinations, as well (‘ld’? 9’)). ,, Sd, E( T ) + 2 < G : f f+l K,, YPA;.
LIPPERT ET AL. I , 3 I 5 I 6 I 1031~- 1031T~ Fig. 8. Temperature dependence of the quantum yields of B fluorescence (&) and A fluorescence (4A)of DMABN in n-butyl chloride (data from Fig. 1). From the slopes, the formal activation energies E , and E, for B*+A* and reverse reaction, respectively, can be derived. thus due to the energetic stabilization of the A* state, the larger part results from the energy destabilization of the twisted ground state owing to combined effects of ground-state intramolecular rotational barrier and intermolecular solute-solvent interactions directly after photon emission.
Advances in Chemical Physics, Vol. 68 by Ilya Prigogine