Condensed-phase system quantum numerical solution

In this section we present some applications of the LAND-map approach for computing time correlation functions and time dependent quantum expectation values for realistic model condensed phase systems. These representative applications demonstrate how the methodology can be implemented in general and provide challenging tests of the approach. The first test application is the spin-boson model where exact results are known from numerical path integral calculations [59-62]. The second system we study is a fully atomistic model for excess electronic transport in metal - molten salt solutions. Here the potentials are sufficiently reliable that findings from our calculations can be compared with experimental results. 

Abstract The computational study of excited states of molecular systems in the condensed phase implies additional complications with respect to analogous studies on isolated molecules. Some of them can be faced by a computational modeling based on a continuum (i.e., implicit) description of the solvent. Among this class of methods, the polarizable continuum model (PCM) has widely been used in its basic formulation to study ground state properties of molecular solutes. The consideration of molecular properties of excited states has led to the elaboration of numerous additional features not present in the PCM basic version. Nonequilibrium effects, state-specific versus linear response quantum mechanical description, analytical gradients, and electronic coupling between solvated chromophores are reviewed in the present contribution. The presentation of some selected computational results shows the potentialities of the approach. 

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