Reorientation dynamics of electronic orbitals in condensed phases. Simulations of F(²P) atoms in solid Kr

Transitions induced by lattice motions between different electronic states of an F(²P) atom in solid Kr are studied by molecular dynamics simulations. Hopping between potential surfaces is used in modelling the electronic transitions. Calculations for an initially prepared p-orbital orientation, with the lattice at T = 25 K, show (1) the decay of orbital orientation at short times (t≤40 fs) is well described by a model of random, uncorrelated surface hopping events; (2) the probability of orbital reorientation events is highly correlated with lattice cage distortions of a particular symmetry type, and weakly correlated with cage radial breathing motions; (3) the rate of electronic transitions is nearly constant in time at thermal conditions.