A semiempirical effective Hamiltonian based approach for analyzing excited state wave functions and computing excited state absorption spectra using real-time dynamics

Soumen Ghosh, Jason C. Asher, Laura Gagliardi, Chris Cramer, Niranjan Govind

Research output: Contribution to journalArticle

Abstract

We describe a new approach to extract information about an excited state wave function using a reduced orbital space molecular orbital decomposition approach for time-dependent density obtained from real-time dynamics. We also show how this information about the excited state wave function can be used to accelerate the convergence of real-time spectra and model excited state electron dynamics. We have combined this approach with our recent implementation of the real-time intermediate neglect of differential overlap for spectroscopy (INDO/S) to study the solvatochromic shift of Nile Red in acetone, ethanol, toluene and n-hexane solvents, and, for the first time, the excited state absorption spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine, and nickel TPyP using a semiempirical Hamiltonian.

Original languageEnglish (US)
Article number104103
JournalJournal of Chemical Physics
Volume150
Issue number10
DOIs
StatePublished - Mar 14 2019

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Hamiltonians
Wave functions
Excited states
Absorption spectra
wave functions
absorption spectra
porphyrins
excitation
Porphyrins
Toluene
Molecular orbitals
Acetone
Nickel
acetone
toluene
molecular orbitals
ethyl alcohol
Ethanol
zinc
nickel

PubMed: MeSH publication types

  • Journal Article

Cite this

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abstract = "We describe a new approach to extract information about an excited state wave function using a reduced orbital space molecular orbital decomposition approach for time-dependent density obtained from real-time dynamics. We also show how this information about the excited state wave function can be used to accelerate the convergence of real-time spectra and model excited state electron dynamics. We have combined this approach with our recent implementation of the real-time intermediate neglect of differential overlap for spectroscopy (INDO/S) to study the solvatochromic shift of Nile Red in acetone, ethanol, toluene and n-hexane solvents, and, for the first time, the excited state absorption spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine, and nickel TPyP using a semiempirical Hamiltonian.",
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AU - Ghosh, Soumen

AU - Asher, Jason C.

AU - Gagliardi, Laura

AU - Cramer, Chris

AU - Govind, Niranjan

PY - 2019/3/14

Y1 - 2019/3/14

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AB - We describe a new approach to extract information about an excited state wave function using a reduced orbital space molecular orbital decomposition approach for time-dependent density obtained from real-time dynamics. We also show how this information about the excited state wave function can be used to accelerate the convergence of real-time spectra and model excited state electron dynamics. We have combined this approach with our recent implementation of the real-time intermediate neglect of differential overlap for spectroscopy (INDO/S) to study the solvatochromic shift of Nile Red in acetone, ethanol, toluene and n-hexane solvents, and, for the first time, the excited state absorption spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine, and nickel TPyP using a semiempirical Hamiltonian.

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