Quantum initial condition sampling for linearized density matrix dynamics: Vibrational pure dephasing of iodine in krypton matrices

Abstract

This paper reviews the linearized path integral approach for computing time dependent properties of systems that can be approximated using a mixed quantum-classical description. This approach is applied to studying vibrational pure dephasing of ground state molecular iodine in a rare gas matrix. The Feynman-Kleinert optimized harmonic approximation for the full system density operator is used to sample initial conditions for the bath degrees of freedom. This extremely efficient approach is compared to alternative initial condition sampling techniques at low temperatures where classical initial condition sampling yields dephasing rates that are nearly an order of magnitude too slow compared to quantum initial condition sampling and experimental results.