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arXiv · 1812.08827

Simulating X-ray absorption spectra with linear-response density cumulant theory

Ruojing Peng·Andreas V. Copan·Alexander Yu. Sokolov
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Abstract

We present a new approach for simulating X-ray absorption spectra based on linear-response density cumulant theory (LR-DCT) [A. V. Copan and A. Yu. Sokolov, J. Chem. Theory Comput., 2018, 14, 4097 - 4108]. Our new method combines the LR-ODC-12 formulation of LR-DCT with core-valence separation approximation (CVS) that allows to efficiently access high-energy core-excited states. We describe our computer implementation of the CVS-approximated LR-ODC-12 method (CVS-ODC-12) and benchmark its performance by comparing simulated X-ray absorption spectra to those obtained from experiment for several small molecules. Our results demonstrate that the CVS-ODC-12 method shows a good agreement with experiment for relative spacings between transitions and their intensities, but the excitation energies are systematically overestimated. When comparing to results from excited-state coupled cluster methods with single and double excitations, the CVS-ODC-12 method shows a similar performance for intensities and peak separations, while coupled cluster spectra are less shifted, relative to experiment. An important advantage of CVS-ODC-12 is that its excitation energies are computed by diagonalizing a Hermitian matrix, which enables efficient computation of transition intensities.

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Ruojing Peng, Andreas V. Copan, Alexander Yu. Sokolov. 2018-12-20. Simulating X-ray absorption spectra with linear-response density cumulant theory. https://doi.org/10.1021/acs.jpca.8b12259

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