An exact representation of quantum mechanics using the language of phase-space variables provides a natural starting point to introduce and develop semiclassical approximations for the calculation of time correlation functions. Here, we introduce an exact path-integral formalism for calculations of multi-time quantum correlation functions as canonical averages over ring-polymer dynamics in imaginary time. The formulation provides a general formalism that exploits the symmetry of path integrals with respect to permutations in imaginary time, expressing correlations as products of imaginary-time-translation-invariant phase-space functions coupled through Poisson bracket operators. The method naturally recovers the classical limit of multi-time correlation functions and provides an interpretation of quantum dynamics in terms of “interfering trajectories” of the ring-polymer in phase space. The introduced phase-space formulation provides a rigorous framework for the future development of quantum dynamics methods that exploit the invariance of imaginary time path integrals to cyclic permutations.
Imaginary-time open-chain path-integral approach for two-state time correlation functions and applications in charge transfer
Quantum time correlation functions (TCFs) involving two states are important for describing nonadiabatic dynamical processes such as charge transfer (CT). Based on a previous single-state method, we propose an imaginary-time open-chain path-integral (OCPI) approach for evaluating the two-state symmetrized TCFs. Expressing the forward and backward propagation on different electronic potential energy surfaces as a complex-time path integral, we then transform the path variables to average and difference variables such that the integration over the difference variables up to the second order can be performed analytically. The resulting expression for the symmetrized TCF is equivalent to sampling the open-chain configurations in an effective potential that corresponds to the average surface. Using importance sampling over the extended OCPI space via open path-integral molecular dynamics, we tested the resulting path-integral approximation by calculating the Fermi’s golden rule CT rate constant within a widely used spin-boson model. Comparing with the real-time linearized semiclassical method and analytical result, we show that the imaginary-time OCPI provides an accurate two-state symmetrized TCF and rate constant in the typical turnover region. It is shown that the first bead of the open chain corresponds to physical zero-time and that the endpoint bead corresponds to final time t; oscillations of the end-to-end distance perfectly match the nuclear mode frequency. The two-state OCPI scheme is seen to capture the tested model’s electronic quantum coherence and nuclear quantum effects accurately.
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- Award ID(s):
- 1955381
- NSF-PAR ID:
- 10401655
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 11
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 114111
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0098162
