Accurate density functional calculations of near-edge x-ray and optical absorption spectra of liquid water using nonperiodic boundary conditions: the role of self-interaction and long-range effects.
An integrated theoretical approach based on a discrete-continuum solvent model combined with molecular dynamics and time-dependent density functional theory leads to near-edge x-ray and optical absorption spectra of liquid water in excellent agreement with experiments. For quantitative results both self-interaction and long-range effects should be properly corrected. While scaling with respect to a monomer effectively compensates the self-interaction error, long-range effects require inclusion of exact exchange. Further, new physical insights on the not fully elucidated nature of the first optical band are provided.
Brancato
Giuseppe
G
Dipartimento di Chimica, Università Federico II, Complesso Universitario di Monte S. Angelo, via Cintia, I-80126 Napoli, Italy.
Rega
Nadia
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Barone
Vincenzo
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