AIMSWISS—Ab initio multiple spawning with informed stochastic selections

Lassmann, Yorick; Curchod, Basile F.E.

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

Citation

Lassmann, Y., & Curchod, B. F. (2021). AIMSWISS—Ab initio multiple spawning with informed stochastic selections. The Journal of Chemical Physics, 154(21), https://doi.org/10.1063/5.0052118

• Journal Article Type: Article
• Acceptance Date: May 17, 2021
• Online Publication Date: Jun 3, 2021
• Publication Date: Jun 7, 2021
• Deposit Date: Jun 7, 2021
• Publicly Available Date: Jun 8, 2021
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 154
• Issue: 21
• DOI: https://doi.org/10.1063/5.0052118
• Public URL: https://durham-repository.worktribe.com/output/1241584