Nonadiabatic Ring Polymer Molecular Dynamics for the Description of Biological Electron and Proton Transfer Processes
Final Report Abstract
The quantum-mechanical motion of electrons and nuclei underlies the physical and chemical processes in modern quantum information and energy conversion technologies. The control and manipulation of quantum computers, the measurement of tiny nanoscale objects, the catalysis at surfaces, and the harnessing of novel energy resources all require an in-depth understanding of the quantum dynamics that governs the flow of energy and information. In this DFG project, we developed new methods for the theoretical description of quantum dynamics in photo-chemical, charge-transfer, and energy-transfer processes in the gas and condensed phases. The new methods quantize the nuclei using a path-integral representation that maps the quantum nuclei onto classical ring polymers, necklaces of beads connected via harmonic springs. The electrons are described fully quantum-mechanically by an electronic wavefunction, and the ring polymers of the quantized nuclei move on many potential energy surfaces with nonadiabatic transitions implemented via surface hops. We have also extended the pathintegral based methods to simulate dynamics with non-thermal quantum statistical distributions, such as the fixed total energy, microcanonical distribution. The novel approach establishes a ring polymer temperature in terms of the microcanonical fixed total energy via the stationary phase approximation to the inverse Laplace transform, preserving the stability and computational affordability of the imaginary-time path-integral based methods for condensed phase quantum dynamics.
Publications
- J. Chem. Phys. 148, 102327 (2018)
X. Tao, Ph. Shushkov, and T. F. Miller III
(See online at https://doi.org/10.1063/1.5005544) - J. Chem. Phys. 151, 134107 (2019)
Ph. Shushkov, and T. F. Miller III
(See online at https://doi.org/10.1063/1.5121749) - J. Phys. Chem. A 123, 3013 (2019)
X. Tao, Ph. Shushkov, and T. F. Miller III
(See online at https://doi.org/10.1021/acs.jpca.9b00877) - Nature Commun. 10, 2294 (2019)
Y. Yao, Ph. Shushkov, T. F. Miller III, and K. P. Giapis
(See online at https://doi.org/10.1038/s41467-019-10342-6) - J. Chem. Phys. 152, 124117 (2020)
X. Tao, Ph. Shushkov, and T. F. Miller III
(See online at https://doi.org/10.1063/1.5144307)
