Abstract
We present a detailed study of the decoherence correction to surface hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and the same electronic structure method are used as a reference for three molecules: ethylene, the methaniminium cation, and fulvene, for which nonadiabatic dynamics follows a photoexcitation. A comparison with the Granucci-Persico energy-based decoherence correction and the augmented fewest-switches surface-hopping scheme shows that the three decoherence-corrected methods operate on individual trajectories in a qualitatively different way, but the results averaged over trajectories are similar for these systems.
| Original language | English |
|---|---|
| Pages (from-to) | 3852-3862 |
| Number of pages | 11 |
| Journal | Journal of Chemical Theory and Computation |
| Volume | 17 |
| Issue number | 7 |
| Early online date | 17 Jun 2021 |
| DOIs | |
| Publication status | Published - 13 Jul 2021 |
Bibliographical note
Funding Information:This work was primarily supported by the Computational Chemical Center: Chemistry in Solution and at Interfaces funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0019394 (P.V.Z.) as part of the Computational Chemical Sciences Program. This grant also applies for the calculations carried out on Temple University’s HPC resources. Partial support from the Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under award no. DESC0020044 (N.T.M.) is also acknowledged. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 803718, project SINDAM). L.M.I. acknowledges the EPSRC for an EPSRC Doctoral Studentship (EP/R513039/1). P.V. and N.T.M. thank Spiridoula Matsika for useful conversations.
Funding Information:
This work was primarily supported by the Computational Chemical Center: Chemistry in Solution and at Interfaces funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0019394 (P.V.Z.) as part of the Computational Chemical Sciences Program. This grant also applies for the calculations carried out on Temple Universit's HPC resources. Partial support from the Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under award no. DESC0020044 (N.T.M.) is also acknowledged. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 803718, project SINDAM). L.M.I. acknowledges the EPSRC for an EPSRC Doctoral Studentship (EP/R513039/1). P.V. and N.T.M. thank Spiridoula Matsika for useful conversations.
Publisher Copyright:
© 2021 American Chemical Society.