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Issue 22, 2015
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Simulation of X-ray absorption spectra with orthogonality constrained density functional theory

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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

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The article was received on 27 Nov 2014, accepted on 26 Jan 2015 and first published on 27 Jan 2015


Article type: Paper
DOI: 10.1039/C4CP05509H
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 14360-14374
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    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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