On the identity of the identity operator in nonadiabatic linearized semiclassical dynamics.
- Saller MAC Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich, Switzerland.
- Kelly A Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada.
- Richardson JO Laboratory of Physical Chemistry, ETH Zurich, 8093 Zurich, Switzerland.
- 2019-02-24
Published in:
- The Journal of chemical physics. - 2019
English
Simulating the nonadiabatic dynamics of condensed-phase systems continues to pose a significant challenge for quantum dynamics methods. Approaches based on sampling classical trajectories within the mapping formalism, such as the linearized semiclassical initial value representation (LSC-IVR), can be used to approximate quantum correlation functions in dissipative environments. Such semiclassical methods however commonly fail in quantitatively predicting the electronic-state populations in the long-time limit. Here we present a suggestion to minimize this difficulty by splitting the problem into two parts, one of which involves the identity and treating this operator by quantum-mechanical principles rather than with classical approximations. This strategy is applied to numerical simulations of spin-boson model systems, showing its potential to drastically improve the performance of LSC-IVR and related methods with no change in the equations of motion or the algorithm in general, but rather by simply using different functional forms of the observables.
- Language
-
- English
- Open access status
- bronze
- Identifiers
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- DOI 10.1063/1.5082596
- PMID 30795664
- Persistent URL
- https://sonar.ch/global/documents/76033
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