arXiv subjects
Publications and source records attributed to Robert Karrlein.
A theory of vibrational energy relaxation based on a semiclassical treatment of the quantum master equation is presented. Using new results on the semiclassical expansion of dipole matrix elements, we show that in the classical limit the master equation reduces to the Zwanzig energy diffusion equation. The leading quantum corrections are determined and discussed for the harmonic and Morse potentials.
Using the exact path integral solution for the damped harmonic oscillator it is shown that in general there does not exist an exact dissipative Liouville operator describing the dynamics of the oscillator for arbitrary initial bath preparations. Exact non-stationary Liouville operators can be found only for particular preparations. Three physically meaningful examples are examined. An exact new master equation is derived for thermal initial conditions. Second, the Liouville operator governing the time-evolution of equilibrium correlations is obtained. Third, factorizing initial conditions are studied. Additionally, one can show that there are approximate Liouville operators independent of the initial preparation describing the long time dynamics under appropriate conditions. The general form of these approximate master equations is derived and the coefficients are determined for special cases of the bath spectral density including the Ohmic, Drude and weak coupling cases. The connection with earlier work is discussed.