Abstract
Recently we introduced a norm-preserving wavefunction interpolation (NPI) method which allows the accurate and efficient integration of the time-dependent Schrödinger equation in regions of rapidly varying time-derivative coupling (TDC), e.g. near conical intersections (CIs) and effectively (N-1)-dimensional trivial unavoided crossings (TUCs). Herein we report the implementation of the NPI scheme into the ab initio multiple spawning (AIMS) method and investigate its behavior in two test systems: one which exhibits a CI and another which exhibits a TUC. In the CI case, AIMS-NPI predicts transfer probabilities that agree to within 0.6% of simulations based on the analytical evaluation of the nonadiabatic couplings, without the need for computationally expensive adaptive integration. In the TUC case, AIMS-NPI results in less than 0.08% error in the population transfer probability when a 0.12 fs time step is used, while simulations based on the analytical approach exhibit catastrophic errors for all finite time steps.
| Original language | English |
|---|---|
| Pages (from-to) | 117-124 |
| Number of pages | 8 |
| Journal | Chemical Physics |
| Volume | 460 |
| DOIs | |
| State | Published - Oct 16 2015 |
Keywords
- Ab initio multiple spawning
- Conical intersection
- Nonadiabatic coupling matrix element
- Nonadiabatic molecular dynamics
- Time-derivative coupling
- Trivial unavoided crossing
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