Simulating X‑ray Absorption Spectra with Linear-Response Density Cumulant Theory

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2019-03, Vol.123 (9), p.1840-1850
• Main Authors: Peng, Ruojing, Copan, Andreas V, Sokolov, Alexander Yu
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.8b12259

We present a new approach for simulating X-ray absorption spectra based on linear-response density cumulant theory (LR-DCT) [ Copan, A. V. ; Sokolov, A. Yu. 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 us 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 good agreement with experiment for relative spacings between transitions and their intensities, but the excitation energies are systematically overestimated. When compared 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.