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Elsevier, Journal of Electron Spectroscopy and Related Phenomena, 2-3(177), p. 135-157

DOI: 10.1016/j.elspec.2010.02.004

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Theoretical approximations to X-ray absorption spectroscopy of liquid water and ice

Journal article published in 2010 by M. Leetmaa, M. P. Ljungberg, A. Lyubartsev, A. Nilsson, L. G. M. Pettersson ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

We review methods to compute X-ray absorption spectra (XAS) with special focus on the transition-potential approach of Triguero et al. [Phys. Rev. B 58 (1998) 8097] and its application to calculations on water in condensed phase. We discuss the absolute energy scale, functional dependence, broadening versus sampling of intra- and intermolecular vibrational modes, treatment of the continuum, cluster size convergence as well as compare with periodic calculations and with experiment; periodic and cluster model calculations are found to agree very closely in the relevant near-edge region although neither reproduces the pre-edge and main-edge features in the experimental spectra of thin ice films. The real-space grid representation of the wave function in the periodic calculations allows a more extended energy range to be described and we find satisfactory agreement with experiment for higher energy continuum resonances. Two proposed alternative approaches using either the potential from a full core-hole (FCH) or the full core-hole with an excited electron in the lowest state (XCH) are shown to lead to spectra that deviate significantly from experiment.