## Abstract

Trajectory surface hopping (TSH) methods have been widely used for the study of nonadiabatic molecular dynamics. In the present work, the accuracy of two TSH algorithms, Tully's fewest switching algorithm and an algorithm based on the Landau-Zener formula, has been critically evaluated in comparison with exact nonadiabatic quantum dynamics calculations for a model of the photoinduced hydrogen-atom dissociation reaction in phenol. The model consists of three electronic states (S_{0}, ^{1}ππ^{∗}, ^{1}πσ^{∗}) and two nuclear degrees of freedom (the OH stretching coordinate and CCOH dihedral angle) and displays two successive conical intersections (^{1}ππ^{∗}/^{1}πσ^{∗} and ^{1}πσ^{∗}/S_{0}). Considering instantaneous photoexcitation from different vibrational levels of the S_{0} state to the ^{1}ππ^{∗} state, we examined the time-dependent electronic population dynamics as well as the branching ratio of the two dissociation channels. The results of fully converged trajectory calculations are compared with the results of exact quantum wave-packet calculations. It is found that both TSH algorithms describe the dynamics at the ^{1}πσ^{∗}/S_{0} conical intersection, which is accessed with high excess energy, with good accuracy. The ^{1}ππ^{∗}/^{1}πσ^{∗} conical intersection, on the other hand, is accessed with little excess energy so tunneling effects as well as wave-packet interference effects which cannot be reproduced with classical trajectory calculations become relevant. Overall, the performance of the fewest-switching and Landau-Zener surface-hopping algorithms for the photodissociation of phenol is very similar. The populations of the adiabatic S_{1} and S_{2} states are found to exhibit fast oscillations which reflect nonadiabatic electronic transitions driven by coherent dynamics in the OH stretching mode. These electronic population oscillations are qualitatively reproduced by both TSH algorithms.

Original language | English |
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Article number | 184114 |

Journal | Journal of Chemical Physics |

Volume | 147 |

Issue number | 18 |

DOIs | |

State | Published - 14 Nov 2017 |