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Title: Real time propagation of the exact two component time-dependent density functional theory

Authors:
; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1324365
Grant/Contract Number:
SC0006863
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 10; Related Information: CHORUS Timestamp: 2016-12-25 21:13:31; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Goings, Joshua J., Kasper, Joseph M., Egidi, Franco, Sun, Shichao, and Li, Xiaosong. Real time propagation of the exact two component time-dependent density functional theory. United States: N. p., 2016. Web. doi:10.1063/1.4962422.
Goings, Joshua J., Kasper, Joseph M., Egidi, Franco, Sun, Shichao, & Li, Xiaosong. Real time propagation of the exact two component time-dependent density functional theory. United States. doi:10.1063/1.4962422.
Goings, Joshua J., Kasper, Joseph M., Egidi, Franco, Sun, Shichao, and Li, Xiaosong. 2016. "Real time propagation of the exact two component time-dependent density functional theory". United States. doi:10.1063/1.4962422.
@article{osti_1324365,
title = {Real time propagation of the exact two component time-dependent density functional theory},
author = {Goings, Joshua J. and Kasper, Joseph M. and Egidi, Franco and Sun, Shichao and Li, Xiaosong},
abstractNote = {},
doi = {10.1063/1.4962422},
journal = {Journal of Chemical Physics},
number = 10,
volume = 145,
place = {United States},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4962422

Citation Metrics:
Cited by: 3works
Citation information provided by
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  • Mechanism of the ring-opening transformation in the photoexcited crystalline benzene is investigated on the femtosecond scale by a computational method based on the real-time propagation (RTP) time-dependent density functional theory (TDDFT). The excited-state dynamics of the benzene molecule is also examined not only for the distinction between the intrinsic properties of molecule and the intermolecular interaction but for the first validation using the vibration frequencies for the RTP-TDDFT approach. It is found that the vibration frequencies of the excited and ground states in the molecule are well reproduced. This demonstrates that the present method of time evolution using the Suzuki-Trotter-typemore » split operator technique starting with the Franck-Condon state approximated by the occupation change of the Kohn-Sham orbitals is adequately accurate. For the crystalline benzene, we carried out the RTP-TDDFT simulations for two typical pressures. At both pressures, large swing of the C-H bonds and subsequent twist of the carbon ring occurs, leading to tetrahedral (sp{sup 3}-like) C-H bonding. The {nu}{sub 4} and {nu}{sub 16} out-of-plane vibration modes of the benzene molecule are found mostly responsible for these motions, which is different from the mechanism proposed for the thermal ring-opening transformation occurring at higher pressure. Comparing the results between different pressures, we conclude that a certain increase of the intermolecular interaction is necessary to make seeds of the ring opening (e.g., radical site formation and breaking of the molecular character) even with the photoexcitation, while the hydrogen migration to fix them requires more free volume, which is consistent with the experimental observation that the transformation substantially proceeds on the decompression.« less
  • The effects of the adiabatic approximation in time-dependent density-functional theory (TDDFT) on dynamic polarizabilities and van der Waals C{sub 6} coefficients have been analyzed quantitatively. These effects are shown to be small in the off-resonance region of the perturbation frequencies by comparing the results from the exact-exchange TDDFT employing the optimized effective potentials and the corresponding frequency-dependent kernel [time-dependent optimized effective potentials (TDOEP)] and those from the frequency-independent kernel [adiabatic TDOEP (ATDOEP)]. The magnitude of the computed dynamic polarizabilities near the static limit is found to be in the order: time-dependent Hartree-Fock (TDHF)>ATDOEP>TDOEP, whereas that of C{sub 6} is: TDHF>TDOEP>ATDOEP.
  • Time-ordered superoperators are used to develop a unified description of nonlinear density response and spontaneous fluctuations of many-electron systems. The pth-order density response functions are decomposed into 2{sup p+1} non-causal Liouville space pathways. Individual pathways are symmetric to the interchange of their space, time, and superoperator indices and can thus be calculated as functional derivatives. Other combinations of these pathways represent spontaneous density fluctuations and the response of such fluctuations to an external field. The resolution of the causality paradox of time-dependent density-functional theory (TDDFT) is shown to be intimately connected with the nonretarded nature of fluctuations.