# Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

## Abstract

Real-time time-dependent density functional theory (RT-TDDFT) is a powerful tool for obtaining spectroscopic observables and understanding complex, time-dependent properties. Currently, performing RT-TDDFT calculations on large, fully quantum mechanical systems is not computationally feasible. Previously, polarizable mixed quantum mechanical and molecular mechanical (QM/MMPol) models have been successful in providing accurate, yet efficient, approximations to a fully quantum mechanical system. Here, we develop a coupling scheme between induced dipole based QM/MMPol and RT-TDDFT. Our approach is validated by comparing calculated spectra with both real-time and linear-response TDDFT calculations. Here, the model developed within provides an accurate method for performing RT-TDDFT calculations on extended systems while accounting for mutual polarization between the quantum mechanical and molecular mechanical regions.

- Authors:

- Univ. of Washington, Seattle, WA (United States)
- Univ. di Pisa (Italy)

- Publication Date:

- Research Org.:
- Univ. of Washington, Seattle, WA (United States)

- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)

- OSTI Identifier:
- 1594491

- Grant/Contract Number:
- [SC0006863; CHE-1565520; MRI-1624430]

- Resource Type:
- Accepted Manuscript

- Journal Name:
- Journal of Physical Chemistry Letters

- Additional Journal Information:
- [ Journal Volume: 8; Journal Issue: 21]; Journal ID: ISSN 1948-7185

- Publisher:
- American Chemical Society

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electrical properties; Time dependant density functional theory; Molecular structure; Chemical calculations; Polarization

### Citation Formats

```
Donati, Greta, Wildman, Andrew, Caprasecca, Stefano, Lingerfelt, David B., Lipparini, Filippo, Mennucci, Benedetta, and Li, Xiaosong. Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field. United States: N. p., 2017.
Web. doi:10.1021/acs.jpclett.7b02320.
```

```
Donati, Greta, Wildman, Andrew, Caprasecca, Stefano, Lingerfelt, David B., Lipparini, Filippo, Mennucci, Benedetta, & Li, Xiaosong. Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field. United States. doi:10.1021/acs.jpclett.7b02320.
```

```
Donati, Greta, Wildman, Andrew, Caprasecca, Stefano, Lingerfelt, David B., Lipparini, Filippo, Mennucci, Benedetta, and Li, Xiaosong. Tue .
"Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field". United States. doi:10.1021/acs.jpclett.7b02320. https://www.osti.gov/servlets/purl/1594491.
```

```
@article{osti_1594491,
```

title = {Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field},

author = {Donati, Greta and Wildman, Andrew and Caprasecca, Stefano and Lingerfelt, David B. and Lipparini, Filippo and Mennucci, Benedetta and Li, Xiaosong},

abstractNote = {Real-time time-dependent density functional theory (RT-TDDFT) is a powerful tool for obtaining spectroscopic observables and understanding complex, time-dependent properties. Currently, performing RT-TDDFT calculations on large, fully quantum mechanical systems is not computationally feasible. Previously, polarizable mixed quantum mechanical and molecular mechanical (QM/MMPol) models have been successful in providing accurate, yet efficient, approximations to a fully quantum mechanical system. Here, we develop a coupling scheme between induced dipole based QM/MMPol and RT-TDDFT. Our approach is validated by comparing calculated spectra with both real-time and linear-response TDDFT calculations. Here, the model developed within provides an accurate method for performing RT-TDDFT calculations on extended systems while accounting for mutual polarization between the quantum mechanical and molecular mechanical regions.},

doi = {10.1021/acs.jpclett.7b02320},

journal = {Journal of Physical Chemistry Letters},

number = [21],

volume = [8],

place = {United States},

year = {2017},

month = {10}

}

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