Multiple potential energy surfaces

Hammes-Schiffer S and Tully J C 1995 Nonadiabatic transition state theory and multiple potential energy surfaces molecular dynamics of infrequent events J. Chem. Phys. 103 8528... 

In the previous sections it has been implicitly assumed that the unimolecular reaction is electronically adiabatic and, thus, occurs on a single potential energy surface. Electronically excited states (i.e., multiple potential energy surfaces) for unimolecular reactions was discussed in chapter 3 and it is assumed that the reader has read and is familiar with this material (Nikitin, 1974 Hirst, 1985 Steinfeld et al., 1989). Transitions between electronic states are particularly important for the unimolecular decomposition of ions. For example, the following two dissociation paths ... 

As outlined in the introduction several very efficient single parameter quantum control schemes have been developed and experimentally verified. In this section we will concentrate on the proposals in the time domain. The main idea here is to steer the time evolution of a vibrational wavepacket—either on one potential energy surface or via multiple potential energy surfaces—from the reactant to the product. We will sketch from the theoretical point of view the way from single parameter to multiparameter control. 

D. G. Truhlar, Multiple potential energy surfaces for reactions of species in degenerate electronic states, J. Chem. Phys. 56 3189 (1972), 61 440(E) (1974). 

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