Studies of spuriously shifting resonances in timedependent density functional theory
Adiabatic approximations in timedependent density functional theory (TDDFT) will in general yield unphysical timedependent shifts in the resonance positions of a system driven far from its groundstate. This spurious timedependence is explained in Fuks et al. [Phys. Rev. Lett. 114, 183002 (2015)] in terms of the violation of an exact condition by the nonequilibrium exchangecorrelation 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 timedependent 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 KohnSham 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, chargetransfer across a longrange molecule is hampered, and we show how adjusting the frequencymore »
 Authors:

^{[1]};
^{[2]};
^{[2]}
 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
 City Univ. (CUNY), NY (United States). Dept. of Physics and Astronomy
 Publication Date:
 Grant/Contract Number:
 SC0015344; CHE1152784; CNS0855217; CNS0958379
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 145; Journal Issue: 4; Journal ID: ISSN 00219606
 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) (SC22). 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 timedependent 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 timedependent 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 timedependent 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 timedependent density functional theory},
author = {Luo, Kai and Fuks, Johanna I. and Maitra, Neepa T.},
abstractNote = {Adiabatic approximations in timedependent density functional theory (TDDFT) will in general yield unphysical timedependent shifts in the resonance positions of a system driven far from its groundstate. This spurious timedependence is explained in Fuks et al. [Phys. Rev. Lett. 114, 183002 (2015)] in terms of the violation of an exact condition by the nonequilibrium exchangecorrelation 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 timedependent 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 KohnSham 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, chargetransfer across a longrange molecule is hampered, and we show how adjusting the frequency of a driving field to match the timedependent shift in the chargetransfer 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}
}