Pe. Maslen et al., AN EFFECTIVE HAMILTONIAN FOR AN ELECTRONICALLY EXCITED SOLUTE IN A POLARIZABLE MOLECULAR-SOLVENT, Molecular physics, 94(4), 1998, pp. 693-706
An effective Hamiltonian suitable for non-adiabatic molecular dynamics
simulations is derived for the low-lying electronic states of a molec
ular ion interacting with an assembly of polarizable solvent molecules
. The Hamiltonian includes both induction and low-frequency dispersion
effects. It is based on a molecular treatment of the solvent, but is
similar to effective Hamiltonians that treat the solvent as a dielectr
ic continuum. The electronic structure of the solute is described in a
space defined by the low-lying electronic states of the isolated mole
cule, and no assumptions are made about the form of the basis states.
The effective Hamiltonian uses distributed multipoles and distributed
transition multipoles, both of which may be obtained from ab initio ca
lculations, to describe the charge distribution and polarizability of
the molecular ion.