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Title: X-ray circular dichroism signals: a unique probe of local molecular chirality

Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.
Authors:
ORCiD logo [1] ;  [1] ; ORCiD logo [2] ;  [3] ;  [1]
  1. Univ. of California, Irvine, CA (United States)
  2. Univ. at Buffalo, State Univ. of New York, Buffalo, NY (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Report Number(s):
PNNL-SA-125728
Journal ID: ISSN 2041-6520; CSHCBM; 49640; KC0301050
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory
OSTI Identifier:
1390446

Zhang, Yu, Rouxel, Jeremy R., Autschbach, Jochen, Govind, Niranjan, and Mukamel, Shaul. X-ray circular dichroism signals: a unique probe of local molecular chirality. United States: N. p., Web. doi:10.1039/c7sc01347g.
Zhang, Yu, Rouxel, Jeremy R., Autschbach, Jochen, Govind, Niranjan, & Mukamel, Shaul. X-ray circular dichroism signals: a unique probe of local molecular chirality. United States. doi:10.1039/c7sc01347g.
Zhang, Yu, Rouxel, Jeremy R., Autschbach, Jochen, Govind, Niranjan, and Mukamel, Shaul. 2017. "X-ray circular dichroism signals: a unique probe of local molecular chirality". United States. doi:10.1039/c7sc01347g. https://www.osti.gov/servlets/purl/1390446.
@article{osti_1390446,
title = {X-ray circular dichroism signals: a unique probe of local molecular chirality},
author = {Zhang, Yu and Rouxel, Jeremy R. and Autschbach, Jochen and Govind, Niranjan and Mukamel, Shaul},
abstractNote = {Core-resonant circular dichroism (CD) signals are induced by molecular chirality and vanish for achiral molecules and racemic mixtures. The highly localized nature of core excitations makes them ideal probes of local chirality within molecules. Simulations of the circular dichroism spectra of several molecular families illustrate how these signals vary with the electronic coupling to substitution groups, the distance between the X-ray chromophore and the chiral center, geometry, and chemical structure. As a result, clear insight into the molecular structure is obtained through analysis of the X-ray CD spectra.},
doi = {10.1039/c7sc01347g},
journal = {Chemical Science},
number = 9,
volume = 8,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

Two-dimensional stimulated resonance Raman spectroscopy of molecules with broadband x-ray pulses
journal, May 2012
  • Biggs, Jason D.; Zhang, Yu; Healion, Daniel
  • The Journal of Chemical Physics, Vol. 136, Issue 17, Article No. 174117
  • DOI: 10.1063/1.4706899

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980
  • McLean, A. D.; Chandler, G. S.
  • The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
  • DOI: 10.1063/1.438980

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994
  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001