### Abstract

Electronic energy flow in an isolated molecular system involves coupling between the electronic and nuclear subsystems, and the coupled system evolves to a statistical mixture of pure states. In semiclassical theories, nuclear motion is treated using classical mechanics, and electronic motion is treated as an open quantal system coupled to a "bath" of nuclear coordinates. We have previously shown how this can be simulated by a time-dependent Schrödinger equation with coherent switching and decay of mixing, where the decay of mixing terms model the dissipative effect of the environment on the electronic subdynamics (i.e., on the reduced dynamics of the electronic subsystem). In the present paper we reformulate the problem as a Liouville-von Neumann equation of motion (i.e., we propagate the reduced density matrix of the electronic subsystem), and we introduce the assumption of first-order linear decay. We specifically examine the cases of equal relaxation times for both longitudinal (i.e., population) decay and transverse decay (i.e., dephasing) and of longitudinal relaxation only, yielding the linear decay of mixing (LDM) and the population-driven decay of mixing (PDDM) schemes, respectively. Because we do not generally know the basis in which coherence decays, that is, the pointer basis, we judge the semiclassical methods in part by their ability to give good results in both the adiabatic and diabatic bases. The accuracy in the prediction of physical observables is shown to be robust not only with respect to basis but also with respect to the way in which demixing is incorporated into the master equation for the density matrix. The success of the PDDM scheme is particularly interesting because it incorporates the least amount of decoherence (i.e., the PDDM scheme is the most similar of the methods discussed to the fully coherent semiclassical Ehrenfest method). For both the new and previous decay of mixing schemes, four kinds of decoherent state switching algorithms are analyzed and compared to one another: natural switching (NS), self-consistent switching (SCS), coherent switching (CS), and globally coherent switching (GCS). The CS formulations are examples of a non-Markovian method, in which the system retains some memory of its history, whereas the GCS, SCS, and NS schemes are Markovian (time local). These methods are tested against accurate quantum mechanical results using 17 multidimensional atom-diatom test cases. The test cases include avoided crossings, conical interactions, and systems with noncrossing diabatic potential energy surfaces. The CS switching algorithm, in which the state populations are controlled by a coherent stochastic algorithm for each complete passage through a strong interaction region, but successive strong-interaction regions are not mutually coherent, is shown to be the most accurate of the switching algorithms tested for the LDM and PDDM methods as well as for the previous decay of mixing methods, which are reformulated here as Liouville-von Neumann equations with nonlinear decay of mixing (NLDM). We also demonstrate that one variant of the PDDM method with CS performs almost equally well in the adiabatic and diabatic representations, which is a difficult objective for semiclassical methods. Thus decay of mixing methods provides powerful mixed quantum-classical methods for modeling non-Born-Oppenheimer polyatomic dynamics including photochemistry, charge-transfer, and other electronically nonadiabatic processes.

Original language | English |
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Pages (from-to) | 527-540 |

Number of pages | 14 |

Journal | Journal of Chemical Theory and Computation |

Volume | 1 |

Issue number | 4 |

DOIs | |

State | Published - 1 Dec 2005 |

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## Cite this

*Journal of Chemical Theory and Computation*,

*1*(4), 527-540. https://doi.org/10.1021/ct050021p