Ov. Prezhdo et Pj. Rossky, EVALUATION OF QUANTUM TRANSITION RATES FROM QUANTUM-CLASSICAL MOLECULAR-DYNAMICS SIMULATIONS, The Journal of chemical physics, 107(15), 1997, pp. 5863-5878
The impact of quantum decoherence and zero point motion on non-adiabat
ic transition rates in condensed matter systems is studied in relation
to non-adiabatic (NA) molecular dynamics (MD) techniques. Both effect
s, and decoherence in particular, strongly influence the transition ra
te, while neither is accounted for by straightforward quantum-classica
l approaches. Quantum corrections to the quantum-classical results are
rigorously introduced based on Kubo's generating function formulation
of Fermi's Golden rule and the frozen Gaussian approximation for the
nuclear wave functions. The development provides a one-to-one correspo
ndence between the decoherence function and the Franck-Condon factor.
The decoherence function defined in this paper corrects an error in ou
r previous work [J. Chem. Phys. 104, 5942 (1996)]. The relationship be
tween the short time approach and the real time NA MD is investigated
and a specific prescription for incorporating quantum decoherence into
NA simulations is given. The proposed scheme is applied to the hydrat
ed electron. The rate of excited state non-radiative relaxation is fou
nd to be very sensitive to the decoherence time. Quantum coherence dec
ays about 50% faster in H2O than in D2O, providing a theoretical ratio
nalization for the lack of experimentally observed solvent isotope eff
ect on the relaxation rate. Microscopic analysis of solvent mode contr
ibutions to the coherence decay shows that librational degrees of free
dom are primarily responsible, due to the strong coupling between the
electron and molecular rotations and to the small widths of the wave p
ackets describing these modes. Zero point motion of the O-H bonds decr
eases the life time of the excited state of the hydrated electron by a
factor of 1.3-1.5. The implications of the use of short time approxim
ations for the NA transition rate and for the evolution of the nuclear
wave functions are considered. (C) 1997 American Institute of Physics
.