Defining the Temperature of an Isolated Molecule

Barbatti, Mario

doi:10.26434/chemrxiv-2022-5kr7s-v2

Cited by 1 publication

(2 citation statements)

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“…Moreover, I have defined clear protocols for the statistical analysis, including introducing the Λ (1,2) score to compare different data sets, and made all raw data readily available. 48 Thus, extensions of this benchmark toward other molecule types and methods may be seamlessly executed.…”

Section: Discussionmentioning

confidence: 99%

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Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

Barbatti

2021

J. Chem. Theory Comput.

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The most common surface hopping dynamics algorithms require velocity adjustment after hopping to ensure total-energy conservation. Based on the semiclassical analysis, this adjustment must be made parallel to the nonadiabatic coupling vector's direction. Nevertheless, this direction is not always known, and the common practice has been to adjust the velocity in either the linear momentum or velocity directions. This paper benchmarks surface hopping dynamics of photoexcited ethylene with velocity adjustment in several directions, including those of the nonadiabatic coupling vector, the momentum, and the energy gradient difference. It is shown that differences in time constants and structural evolution fall within the statistical uncertainty of the method considering up to 500 trajectories in each dynamics set, rendering the three approaches statistically equivalent. For larger ensembles beyond 1000 trajectories, significant differences between the results arise, limiting the validity of adjustment in alternative directions. Other possible adjustment directions (velocity, single-state gradients, angular momentum) are evaluated as well. Given the small size of ethylene, the results reported in this paper should be considered an upper limit for the error caused by the choice of the velocity-adjustment direction on surface hopping dynamics. LJ P L J(4)

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Section: Discussionmentioning

confidence: 99%

“…All Newton-X input and output files for the three sets of dynamics are available for download. 48 II.II. Data Analysis.…”

Section: Introductionmentioning

confidence: 99%