Issue 22, 2015

Simulation of X-ray absorption spectra with orthogonality constrained density functional theory

Abstract

Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree–Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine.

Graphical abstract: Simulation of X-ray absorption spectra with orthogonality constrained density functional theory

Supplementary files

Article information

Article type
Paper
Submitted
27 Nov 2014
Accepted
26 Jan 2015
First published
27 Jan 2015

Phys. Chem. Chem. Phys., 2015,17, 14360-14374

Author version available

Simulation of X-ray absorption spectra with orthogonality constrained density functional theory

W. D. Derricotte and F. A. Evangelista, Phys. Chem. Chem. Phys., 2015, 17, 14360 DOI: 10.1039/C4CP05509H

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