Semiquantal time-dependent Hartree approach to condensed phase chemical dynamics: application to the system-bath model.
A semiquantal analysis of condensed phase chemical dynamics, outlined recently for a double-well linearly coupled to dissipative harmonic bath, is formulated in detail to clarify its general features as well as the specifics of the linear and quadratic coupling cases. The theory may be called a "semiquantal time-dependent Hartree (SQTDH)" approach, as it assumes a factorized product of the squeezed coherent state wave packets for the variational subspace of the many-dimensional time-dependent wave function. Due to this assumption, it straightforwardly satisfies the canonicity condition introduced by Marumori et al. is described by a set of Hamilton equations of motion in an extended phase space that includes auxiliary coordinates representing the wave packet widths. The potential in the extended phase space provides a pictorial understanding of the quantum effects affected due to the bath coupling, e.g., suppression of the wave packet spreading in terms of the potential wall developing along the auxiliary coordinates. The idea is illustrated by prototypical models of quartic double-well and cubic metastable potentials linearly and quadratically coupled to the bath. Further applications and extensions, where the SQTDH method will offer a practical approach for introducing quantum effects into realistic molecular dynamics simulations, are also discussed.
Ando
Koji
K
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, United Kingdom.