AIMSWISS—Ab initio multiple spawning with informed stochastic selections

Yorick Lassmann; Basile F.E. Curchod

doi:10.1063/5.0052118

AIMSWISS—Ab initio multiple spawning with informed stochastic selections

Yorick Lassmann
, Basile F.E. Curchod^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

18 Citations (Scopus)

Abstract

Ab initio multiple spawning (AIMS) offers a reliable strategy to describe the excited-state dynamics and nonadiabatic processes of molecular systems. AIMS represents nuclear wavefunctions as linear combinations of traveling, coupled Gaussians called trajectory basis functions (TBFs) and uses a spawning algorithm to increase as needed the size of this basis set during nonadiabatic transitions. While the success of AIMS resides in this spawning algorithm, the dramatic increase in TBFs generated by multiple crossings between electronic states can rapidly lead to intractable dynamics. In this Communication, we introduce a new flavor of AIMS, coined ab initio multiple spawning with informed stochastic selections (AIMSWISS), which proposes a parameter-free strategy to beat the growing number of TBFs in an AIMS dynamics while preserving its accurate description of nonadiabatic transitions. The performance of AIMSWISS is validated against the photodynamics of ethylene, cyclopropanone, and fulvene. This technique, built upon the recently developed stochastic-selection AIMS, is intended to serve as a computationally affordable starting point for multiple spawning simulations.

Original language	English
Article number	211106
Journal	Journal of Chemical Physics
Volume	154
Issue number	21
DOIs	https://doi.org/10.1063/5.0052118
Publication status	Published - 7 Jun 2021

Bibliographical note

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programm1e (Grant Agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212—Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University. The authors thank Lea M. Ibele and Federica Agostini for fruitful discussions and comments on the manuscript.

Publisher Copyright:
© 2021 Author(s).

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Physical & Theoretical

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title = "AIMSWISS—Ab initio multiple spawning with informed stochastic selections",

abstract = "Ab initio multiple spawning (AIMS) offers a reliable strategy to describe the excited-state dynamics and nonadiabatic processes of molecular systems. AIMS represents nuclear wavefunctions as linear combinations of traveling, coupled Gaussians called trajectory basis functions (TBFs) and uses a spawning algorithm to increase as needed the size of this basis set during nonadiabatic transitions. While the success of AIMS resides in this spawning algorithm, the dramatic increase in TBFs generated by multiple crossings between electronic states can rapidly lead to intractable dynamics. In this Communication, we introduce a new flavor of AIMS, coined ab initio multiple spawning with informed stochastic selections (AIMSWISS), which proposes a parameter-free strategy to beat the growing number of TBFs in an AIMS dynamics while preserving its accurate description of nonadiabatic transitions. The performance of AIMSWISS is validated against the photodynamics of ethylene, cyclopropanone, and fulvene. This technique, built upon the recently developed stochastic-selection AIMS, is intended to serve as a computationally affordable starting point for multiple spawning simulations.",

author = "Yorick Lassmann and Curchod, \{Basile F.E.\}",

note = "Funding Information: This project has received funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation programm1e (Grant Agreement No. 803718, project SINDAM). This article is based upon work from COST Action CA18212—Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology), and made use of the facilities of the Hamilton HPC Service of Durham University. The authors thank Lea M. Ibele and Federica Agostini for fruitful discussions and comments on the manuscript. Publisher Copyright: {\textcopyright} 2021 Author(s).",

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N2 - Ab initio multiple spawning (AIMS) offers a reliable strategy to describe the excited-state dynamics and nonadiabatic processes of molecular systems. AIMS represents nuclear wavefunctions as linear combinations of traveling, coupled Gaussians called trajectory basis functions (TBFs) and uses a spawning algorithm to increase as needed the size of this basis set during nonadiabatic transitions. While the success of AIMS resides in this spawning algorithm, the dramatic increase in TBFs generated by multiple crossings between electronic states can rapidly lead to intractable dynamics. In this Communication, we introduce a new flavor of AIMS, coined ab initio multiple spawning with informed stochastic selections (AIMSWISS), which proposes a parameter-free strategy to beat the growing number of TBFs in an AIMS dynamics while preserving its accurate description of nonadiabatic transitions. The performance of AIMSWISS is validated against the photodynamics of ethylene, cyclopropanone, and fulvene. This technique, built upon the recently developed stochastic-selection AIMS, is intended to serve as a computationally affordable starting point for multiple spawning simulations.

AB - Ab initio multiple spawning (AIMS) offers a reliable strategy to describe the excited-state dynamics and nonadiabatic processes of molecular systems. AIMS represents nuclear wavefunctions as linear combinations of traveling, coupled Gaussians called trajectory basis functions (TBFs) and uses a spawning algorithm to increase as needed the size of this basis set during nonadiabatic transitions. While the success of AIMS resides in this spawning algorithm, the dramatic increase in TBFs generated by multiple crossings between electronic states can rapidly lead to intractable dynamics. In this Communication, we introduce a new flavor of AIMS, coined ab initio multiple spawning with informed stochastic selections (AIMSWISS), which proposes a parameter-free strategy to beat the growing number of TBFs in an AIMS dynamics while preserving its accurate description of nonadiabatic transitions. The performance of AIMSWISS is validated against the photodynamics of ethylene, cyclopropanone, and fulvene. This technique, built upon the recently developed stochastic-selection AIMS, is intended to serve as a computationally affordable starting point for multiple spawning simulations.

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ER -

AIMSWISS—Ab initio multiple spawning with informed stochastic selections

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