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Title: Studies of spuriously shifting resonances in time-dependent density functional theory

Adiabatic approximations in time-dependent density functional theory (TDDFT) will in general yield unphysical time-dependent shifts in the resonance positions of a system driven far from its ground-state. This spurious time-dependence is explained in Fuks et al. [Phys. Rev. Lett. 114, 183002 (2015)] in terms of the violation of an exact condition by the non-equilibrium exchange-correlation kernel of TDDFT. In this work, we give details on the derivation and discuss reformulations of the exact condition that apply in special cases. In its most general form, the condition states that when a system is left in an arbitrary state, the TDDFT resonance position for a given transition in the absence of time-dependent external fields and ionic motion is independent of the state. Special cases include the invariance of TDDFT resonances computed with respect to any reference interacting stationary state of a fixed potential, and with respect to any choice of appropriate stationary Kohn-Sham reference state. We then present several case studies, including one that utilizes the adiabatically exact approximation, that illustrate the conditions and the impact of their violation on the accuracy of the ensuing dynamics. In particular, charge-transfer across a long-range molecule is hampered, and we show how adjusting the frequencymore » of a driving field to match the time-dependent shift in the charge-transfer resonance frequency results in a larger charge transfer over time.« less
Authors:
 [1] ;  [2] ;  [2]
  1. City Univ. (CUNY), NY (United States). Dept. of Physics and Astronomy; Cornell Univ., Ithaca, NY (United States). Baker Lab., Dept. of Chemistry and Chemical Biology
  2. City Univ. (CUNY), NY (United States). Dept. of Physics and Astronomy
Publication Date:
Grant/Contract Number:
SC0015344; CHE-1152784; CNS-0855217; CNS-0958379
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
City Univ. (CUNY), NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; excited states; elgenvalues; external field; computed tomography; ground states; adiabatic theorem; photoexcitations; time dependent density functional theory; charge transfer; orbital dynamics
OSTI Identifier:
1467834
Alternate Identifier(s):
OSTI ID: 1272646

Luo, Kai, Fuks, Johanna I., and Maitra, Neepa T.. Studies of spuriously shifting resonances in time-dependent density functional theory. United States: N. p., Web. doi:10.1063/1.4955447.
Luo, Kai, Fuks, Johanna I., & Maitra, Neepa T.. Studies of spuriously shifting resonances in time-dependent density functional theory. United States. doi:10.1063/1.4955447.
Luo, Kai, Fuks, Johanna I., and Maitra, Neepa T.. 2016. "Studies of spuriously shifting resonances in time-dependent density functional theory". United States. doi:10.1063/1.4955447. https://www.osti.gov/servlets/purl/1467834.
@article{osti_1467834,
title = {Studies of spuriously shifting resonances in time-dependent density functional theory},
author = {Luo, Kai and Fuks, Johanna I. and Maitra, Neepa T.},
abstractNote = {Adiabatic approximations in time-dependent density functional theory (TDDFT) will in general yield unphysical time-dependent shifts in the resonance positions of a system driven far from its ground-state. This spurious time-dependence is explained in Fuks et al. [Phys. Rev. Lett. 114, 183002 (2015)] in terms of the violation of an exact condition by the non-equilibrium exchange-correlation kernel of TDDFT. In this work, we give details on the derivation and discuss reformulations of the exact condition that apply in special cases. In its most general form, the condition states that when a system is left in an arbitrary state, the TDDFT resonance position for a given transition in the absence of time-dependent external fields and ionic motion is independent of the state. Special cases include the invariance of TDDFT resonances computed with respect to any reference interacting stationary state of a fixed potential, and with respect to any choice of appropriate stationary Kohn-Sham reference state. We then present several case studies, including one that utilizes the adiabatically exact approximation, that illustrate the conditions and the impact of their violation on the accuracy of the ensuing dynamics. In particular, charge-transfer across a long-range molecule is hampered, and we show how adjusting the frequency of a driving field to match the time-dependent shift in the charge-transfer resonance frequency results in a larger charge transfer over time.},
doi = {10.1063/1.4955447},
journal = {Journal of Chemical Physics},
number = 4,
volume = 145,
place = {United States},
year = {2016},
month = {7}
}