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Title: An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra

Here, one of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entire ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.
Authors:
 [1] ; ORCiD logo [1]
  1. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Grant/Contract Number:
SC0006863
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 23; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1467568
Alternate Identifier(s):
OSTI ID: 1257291

Goings, Joshua J., and Li, Xiaosong. An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra. United States: N. p., Web. doi:10.1063/1.4953668.
Goings, Joshua J., & Li, Xiaosong. An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra. United States. doi:10.1063/1.4953668.
Goings, Joshua J., and Li, Xiaosong. 2016. "An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra". United States. doi:10.1063/1.4953668. https://www.osti.gov/servlets/purl/1467568.
@article{osti_1467568,
title = {An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra},
author = {Goings, Joshua J. and Li, Xiaosong},
abstractNote = {Here, one of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entire ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.},
doi = {10.1063/1.4953668},
journal = {Journal of Chemical Physics},
number = 23,
volume = 144,
place = {United States},
year = {2016},
month = {6}
}