@article { ISI:A1994PU85600010,
	title = {ADIABATIC APPROXIMATION AND NONADIABATIC EFFECTS FOR OPEN-SHELL ATOMS IN AN INERT SOLVENT - F-ATOMS IN SOLID KR},
	journal = {CHEMICAL PHYSICS},
	volume = {189},
	year = {1994},
	month = {DEC 1},
	pages = {261-272},
	abstract = {The dynamics of P-state F atoms in solid Kr is studied by molecular dynamics simulations in two frameworks: (i) The adiabatic approximation, in which nuclear motion is confined to the lowest adiabatic potential surface of the system; (ii) A method that treats semiclassically non-adiabatic transitions between electronic states in the course of the dynamics. The simulations deal with the spectroscopy of the F atom at different lattice sites, and with orbital reorientation dynamics due to the coupling with lattice vibrations. Also explored is migration of the F atom, following the preparation of an exciplex Kr2+F- which dissociates radiatively in the lattice. Some of the main findings are: (1) p-orbital reorientation dynamics on very short timescales (t less than or similar to 20 fs) is dominated by non-adiabatic mechanisms. Adiabatically, reorientation effects have timescales of the order of 0.25 ps or longer. (2) Lattice vibrations of particular symmetry types are particularly efficient in inducing p-orbital reorientation. (D) Dissociation of a Kr2+F- exciplex can result in migration of the F atom into several lattice sites. The F atom spectroscopy for the different sites is different, and can be experimentally distinguished. (4) The migration probabilities of the F atom calculated adiabatically are much greater than the non-adiabatic ones. The results shed light on the coupling between electron orbital and nuclear dynamics for P-state atoms in solids.},
	issn = {0301-0104},
	doi = {10.1016/0301-0104(94)00322-X},
	author = {Krylov, A. I. and Gerber, R. B. and Apkarian, V. A.}
}
