Red and blue shift of liquid water’s excited states: A many body perturbation study
- Mulliken Center for Theoretical Chemistry, University of Bonn, Bonn (Germany)
In the present paper, accurate optical absorption spectrum of liquid H{sub 2}O is calculated in the energy range of 5–20 eV to probe the nature of water’s excited states by means of many body perturbation approach. Main features of recent inelastic X-ray measurements are well reproduced, such as a bound excitonic peak at 7.9 eV with a shoulder at 9.4 eV as well as the absorption maximum at 13.9 eV, followed by a broad shoulder at 18.4 eV. The spectrum is dominated by excitonic effects impacting the structures of the spectrum at low and higher energy regimes mixed by single particle effects at high energies. The exciton distribution of the low-energy states, in particular of S{sub 1}, is highly anisotropic and localized mostly on one water molecule. The S{sub 1} state is essentially a HOCO-LUCO (highest occupied crystal orbital - lowest unoccupied crystal orbital) transition and of intra-molecular type, showing a localized valence character. Once the excitation energy is increased, a significant change in the character of the electronically excited states occurs, characterized through emergence of multiple quasi-particle peaks at 7.9 eV in the quasi-particle (QP) transition profile and in the occurring delocalized exciton density distribution, spread over many more water molecules. The exciton delocalization following a change of the character of excited states at around 7.9 eV causes the blue shift of the first absorption band with respect to water monomer S{sub 1}. However, due to reduction of the electronic band gap from gas to liquid phase, following enhanced screening upon condensation, the localized S{sub 1} state of liquid water is red-shifted with respect to S{sub 1} state of water monomer. For higher excitations, near vertical ionization energy (11 eV), quasi-free electrons emerge, in agreement with the conduction band electron picture. Furthermore, the occurring red and blue shift of the excited states are independent of the coupling of resonant and anti-resonant contributions to the spectrum.
- OSTI ID:
- 22678988
- Journal Information:
- Journal of Chemical Physics, Vol. 145, Issue 6; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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