Electronic excited states path integral

Figure 28. Time-dependent (a) adiabatic and (b) diabatic electronic excited-state populations as obtained for Model Vb describing electron transfer in solution. Quantum path-integral results [199] (big dots) are compared to mapping results for the limiting cases y = 0 (dashed lines) and Y = 1 (dotted lines) as well as ZPE-adjusted mapping results for Yi p, = 0.3 (full lines).

From the chemically point of view, the valence states are those situated in the chemical zone -and they are the main concern forthe chemical reactivity by employing the frontier or the outer electrons consequently, the semiclas-sical approximation that models the excited states was expressly presented either as an extension of the quantum Feynman path integral or as a specialization of the Feynman-Kleinert formalism for higher temperature treatment of quantum systems (see Section 2.5). However, due to the correspondences of Table 2.1 one may systematically characterize the semiclassical (or quantum chemical) approaches as one of the limiting situations (Putz, 2009) ... 

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