# Ab initio calculation of the electronic absorption spectrum of liquid water

## Abstract

The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of themore »

- Authors:

- Grupo de Física Matemática da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 Lisboa (Portugal)
- (Portugal)
- (Brazil)

- Publication Date:

- OSTI Identifier:
- 22252988

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 16; Other Information: (c) 2014 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 SPECTRA; BORN-OPPENHEIMER APPROXIMATION; DECOMPOSITION; EQUATIONS OF MOTION; EXCITATION; HAMILTONIANS; LIQUIDS; MOLECULAR DYNAMICS METHOD; MONOMERS; POLARIZATION

### Citation Formats

```
Martiniano, Hugo F. M. C., Galamba, Nuno, Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, and Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP.
```*Ab initio calculation of the electronic absorption spectrum of liquid water*. United States: N. p., 2014.
Web. doi:10.1063/1.4871740.

```
Martiniano, Hugo F. M. C., Galamba, Nuno, Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, & Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP.
```*Ab initio calculation of the electronic absorption spectrum of liquid water*. United States. doi:10.1063/1.4871740.

```
Martiniano, Hugo F. M. C., Galamba, Nuno, Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, and Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP. Mon .
"Ab initio calculation of the electronic absorption spectrum of liquid water". United States. doi:10.1063/1.4871740.
```

```
@article{osti_22252988,
```

title = {Ab initio calculation of the electronic absorption spectrum of liquid water},

author = {Martiniano, Hugo F. M. C. and Galamba, Nuno and Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt and Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa and Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP},

abstractNote = {The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase.},

doi = {10.1063/1.4871740},

journal = {Journal of Chemical Physics},

number = 16,

volume = 140,

place = {United States},

year = {Mon Apr 28 00:00:00 EDT 2014},

month = {Mon Apr 28 00:00:00 EDT 2014}

}