Summary
The optical spectrum of water is not well-understood. For example, the main absorption peak shifts upwards by 1.3 eV upon condensation of gas-phase water monomers, which is contrary to the behaviour expected from aggregation-induced broadening of molecular levels. We investigate theoretically the effects of electron-electron and electron-hole correlation, finding that condensation leads to delocalisation of the exciton onto nearby hydrogen-bonded molecules. This reduces its binding energy and has a dramatic impact on the line shape. The calculated spectrum is in excellent agreement with experiment.
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Schmidt, W.G. et al. (2007). Anomalous Water Optical Absorption: Large-Scale First-Principles Simulations. In: Nagel, W.E., Jäger, W., Resch, M. (eds) High Performance Computing in Science and Engineering ’06. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-36183-1_4
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DOI: https://doi.org/10.1007/978-3-540-36183-1_4
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-36165-7
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