# Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes

## Abstract

We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence)

- Authors:

- Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)

- Publication Date:

- OSTI Identifier:
- 22416165

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 8; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ADIABATIC PROCESSES; ALGORITHMS; APPROXIMATIONS; BENCHMARKS; CAPTURE; IMPLEMENTATION; LIFETIME; ONE-DIMENSIONAL CALCULATIONS; POTENTIALS; PROBABILISTIC ESTIMATION; RELAXATION; RELIABILITY; SCATTERING; SURFACES

### Citation Formats

```
Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu.
```*Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes*. United States: N. p., 2015.
Web. doi:10.1063/1.4908032.

```
Ouyang, Wenjun, Dou, Wenjie, & Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu.
```*Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes*. United States. doi:10.1063/1.4908032.

```
Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu. Sat .
"Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes". United States.
doi:10.1063/1.4908032.
```

```
@article{osti_22416165,
```

title = {Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes},

author = {Ouyang, Wenjun and Dou, Wenjie and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu},

abstractNote = {We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence)},

doi = {10.1063/1.4908032},

journal = {Journal of Chemical Physics},

number = 8,

volume = 142,

place = {United States},

year = {Sat Feb 28 00:00:00 EST 2015},

month = {Sat Feb 28 00:00:00 EST 2015}

}