# Self-consistent continuum solvation for optical absorption of complex molecular systems in solution

## Abstract

We introduce a new method to compute the optical absorption spectra of complex molecular systems in solution, based on the Liouville approach to time-dependent density-functional perturbation theory and the revised self-consistent continuum solvation model. The former allows one to obtain the absorption spectrum over a whole wide frequency range, using a recently proposed Lanczos-based technique, or selected excitation energies, using the Casida equation, without having to ever compute any unoccupied molecular orbitals. The latter is conceptually similar to the polarizable continuum model and offers the further advantages of allowing an easy computation of atomic forces via the Hellmann-Feynman theorem and a ready implementation in periodic-boundary conditions. The new method has been implemented using pseudopotentials and plane-wave basis sets, benchmarked against polarizable continuum model calculations on 4-aminophthalimide, alizarin, and cyanin and made available through the QUANTUM ESPRESSO distribution of open-source codes.

- Authors:

- SISSA – Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, 34136 Trieste (Italy)
- Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, Pisa 56126 (Italy)
- Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland)
- (THEOS), École Polytechnique Fédérale de Lausanne, 1015 Lausanne (Switzerland)

- Publication Date:

- OSTI Identifier:
- 22416001

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 3; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ABSORPTION SPECTRA; ALIZARIN; BENCHMARKS; BOUNDARY CONDITIONS; DENSITY FUNCTIONAL METHOD; EV RANGE; EXCITATION; PERIODICITY; PERTURBATION THEORY; POTENTIALS; SOLUTIONS; SOLVATION; TIME DEPENDENCE; WAVE PROPAGATION

### Citation Formats

```
Timrov, Iurii, Biancardi, Alessandro, Andreussi, Oliviero, Marzari, Nicola, Baroni, Stefano, E-mail: baroni@sissa.it, and Theory and Simulation of Materials.
```*Self-consistent continuum solvation for optical absorption of complex molecular systems in solution*. United States: N. p., 2015.
Web. doi:10.1063/1.4905604.

```
Timrov, Iurii, Biancardi, Alessandro, Andreussi, Oliviero, Marzari, Nicola, Baroni, Stefano, E-mail: baroni@sissa.it, & Theory and Simulation of Materials.
```*Self-consistent continuum solvation for optical absorption of complex molecular systems in solution*. United States. doi:10.1063/1.4905604.

```
Timrov, Iurii, Biancardi, Alessandro, Andreussi, Oliviero, Marzari, Nicola, Baroni, Stefano, E-mail: baroni@sissa.it, and Theory and Simulation of Materials. Wed .
"Self-consistent continuum solvation for optical absorption of complex molecular systems in solution". United States.
doi:10.1063/1.4905604.
```

```
@article{osti_22416001,
```

title = {Self-consistent continuum solvation for optical absorption of complex molecular systems in solution},

author = {Timrov, Iurii and Biancardi, Alessandro and Andreussi, Oliviero and Marzari, Nicola and Baroni, Stefano, E-mail: baroni@sissa.it and Theory and Simulation of Materials},

abstractNote = {We introduce a new method to compute the optical absorption spectra of complex molecular systems in solution, based on the Liouville approach to time-dependent density-functional perturbation theory and the revised self-consistent continuum solvation model. The former allows one to obtain the absorption spectrum over a whole wide frequency range, using a recently proposed Lanczos-based technique, or selected excitation energies, using the Casida equation, without having to ever compute any unoccupied molecular orbitals. The latter is conceptually similar to the polarizable continuum model and offers the further advantages of allowing an easy computation of atomic forces via the Hellmann-Feynman theorem and a ready implementation in periodic-boundary conditions. The new method has been implemented using pseudopotentials and plane-wave basis sets, benchmarked against polarizable continuum model calculations on 4-aminophthalimide, alizarin, and cyanin and made available through the QUANTUM ESPRESSO distribution of open-source codes.},

doi = {10.1063/1.4905604},

journal = {Journal of Chemical Physics},

number = 3,

volume = 142,

place = {United States},

year = {Wed Jan 21 00:00:00 EST 2015},

month = {Wed Jan 21 00:00:00 EST 2015}

}