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There is a longstanding difficulty that time-dependent density functional theory relying on adiabatic local density approximation is not applicable to the electron dynamics, for example, for an initially excited state, such as in photochemical reactions. To overcome this, we develop non-adiabatic excited-state time-dependent GW molecular dynamics (TDGW) on the basis of the extended quasiparticle theory. Replacing Kohn–Sham orbitals/energies with correlated, interacting quasiparticle orbitals/energies allows the full correspondence to the excited-state surfaces and corresponding total energies, with satisfying extended Koopmans’ theorem. We demonstrate the power of TDGWusing methane photolysis, CH₄ → CH₃^● + H, an important initiation reaction for combustion/pyrolysis and hydrogen production of methane. We successfully explore several possible pathways and show how this reaction dynamics is captured accurately through simultaneously time-tracing all quasiparticle levels. TDGW scales as O(N_B^3-4), where N_B is the number of basis functions, which is distinctly advantageous to performing dynamics using configuration interaction and coupled cluster methods.

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• In Copyright
  This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Aaditya Manjanath et al., J. Chem. Phys. 160, 184102 (2024) and may be found at https://doi.org/10.1063/5.0202590

Keyword: Molecular dynamics, Methane photolysis, Excited states, time-dependent density functional theory, GW approximation

Date published: 2024-05-14

Publisher: AIP Publishing

Journal:

• The Journal of Chemical Physics (ISSN: 00219606) vol. 160 issue. 18 184102

Funding:

• Institute for Materials Research, Tohoku University 19S0501
• Institute for Materials Research, Tohoku University 20S0505
• Institute for Materials Research, Tohoku University 202308-SCKGE-0216
• Institute for Materials Research, Tohoku University 202212-SCKXX-0506
• Japan Society for the Promotion of Science 21H01607
• Japan Society for the Promotion of Science 21H01877
• National Science, Research and Innovation Fund 90465
• Asian Office of Aerospace Research and Development FA2386-21-1-4024
• Thailand Science Research and Innovation
• Suranaree University of Technology

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1063/5.0202590

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Updated at: 2024-06-06 09:49:16 +0900

Published on MDR: 2025-05-14 08:19:52 +0900