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Title:Path integral methods for quantum dynamics in condensed phases
Author(s):Banerjee, Tuseeta
Director of Research:Makri, Nancy
Doctoral Committee Chair(s):Makri, Nancy
Doctoral Committee Member(s):Hirata, So; Luthey-Schulten, Zan; Schweizer, Kenneth
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Abstract:Quantum mechanical effects play an important role in dynamics of condensed phases. It is also well known that the difficulty of solving the full Schrödinger equation grows exponentially with time. One approach to cope up with this difficulty is to restrict quantum treatment to a few particles (system) and treat the dynamics of the rest of particles (bath) using classical trajectories. Path integral methods due to their trajectory like nature provide excellent tool to develop quantum-classical methods, but to capture long time dynamics, the number of classical trajectories grow exponentially. A part of this work focuses on improving Quantum-Classical Path Integral (QCPI) treatments that allow for larger path integral time step by building “smarter” propagators. These improved solvent-driven reference propagators is developed by incorporating physically motivated approximations to the solvent. When used in QCPI expression they allow convergence with larger time steps leading to an exponential reduction of the number of trajectories required. Further advantages of these propagators include improvements in path filtering techniques, smaller number of path integral steps for achieving the memory decoherence time, and smoothing of the integrand which leads to convergence with fewer Monte Carlo sample points. These ideas have been validated on the spin boson model - a prototypical model to study condensed phase dynamics, which consists of a two-level system coupled to a harmonic bath. The new approach of building the reference propagators combined with their iterative evaluation and filtering is validated using parameters that mimic the first electron transfer in wild-type photosynthetic reaction centres. A real-world dynamical simulation contains various anharmonic effects, Ferrocene (donor) - Ferrocenium (acceptor) system in liquid Benzene was studied where the anharmonic effects of the bath of liquid Benzene on the dynamics of the system were treated using Ensemble Averaged Classical Path. The process of electron or proton transfer occurs between two species having different charges and fluctuations in the solvent plays a key role in determining the rates of such reaction dynamics. To correctly account for the effects of initial distribution of the solvent on the dynamics of the quantum system, the concept of equilibrating the bath to the donor state of the system is used. Two different approaches have been used within the influence functional framework.
Issue Date:2015-12-02
Rights Information:Copyright 2015 Tuseeta Banerjee
Date Available in IDEALS:2016-03-02
Date Deposited:2015-12

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