Issue 9, 2016

Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation

Abstract

The multi-configurational self-consistent field method is employed to simulate the two-dimensional all-X-ray double-quantum-coherence (XDQC) spectroscopy, a four-wave mixing signal that provides direct signatures of double core hole (DCH) states. The valence electronic structure is probed by capturing the correlation between the single (SCH) and double core hole states. The state-averaged restricted-active-space self-consistent field (SA-RASSCF) approach is used which can treat the valence, SCH, and DCH states at the same theoretical level, and applies to all types of DCHs (located on one or two atoms, K-edge or L-edge), with both accuracy and efficiency. Orbital relaxation introduced by the core hole(s) and the static electron correlation is properly accounted for. The XDQC process can take place via different intermediate DCH state channels by tuning the pulse frequencies. We simulate the XDQC signals for the three isomers of aminophenol at 8 pulse frequency configurations, covering all DCH pathways involving the N1s and O1s core hole (N1sN1s, O1sO1s and N1sO1s), which reveal different patterns of valence excitations.

Graphical abstract: Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation

Supplementary files

Article information

Article type
Edge Article
Submitted
09 Apr 2016
Accepted
11 May 2016
First published
12 May 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2016,7, 5922-5933

Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals: a multi-configuration simulation

W. Hua, K. Bennett, Y. Zhang, Y. Luo and S. Mukamel, Chem. Sci., 2016, 7, 5922 DOI: 10.1039/C6SC01571A

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