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; Christopher J. Cramer; Niranjan Govind

doi:10.1063/1.5061746

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
, Christopher J. Cramer
, Niranjan Govind

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

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 language	English (US)
Article number	104103
Journal	Journal of Chemical Physics
Volume	150
Issue number	10
DOIs	https://doi.org/10.1063/1.5061746
State	Published - Mar 14 2019

Bibliographical note

Funding Information:
S.G., C.J.C., and L.G. acknowledge support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award No. DE-FG02-17ER16362. N.G. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and the Office of Advanced Scientific Computing Research through the Scientific Discovery through Advanced Computing (SciDAC) program under Award No. KC-030106062653. S.G. also acknowledges a doctoral dissertation fellowship from the University of Minnesota. The research also benefitted from computational resources provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota and EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle Memorial Institute for the United States Department of Energy under DOE Contract No. DE-AC05-76RL1830. There are no conflicts to declare.

Publisher Copyright:
© 2019 Author(s).

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10.1063/1.5061746

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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.",

author = "Soumen Ghosh and Asher, \{Jason C.\} and Laura Gagliardi and Cramer, \{Christopher J.\} and Niranjan Govind",

note = "Funding Information: S.G., C.J.C., and L.G. acknowledge support from the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award No. DE-FG02-17ER16362. N.G. acknowledges support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and the Office of Advanced Scientific Computing Research through the Scientific Discovery through Advanced Computing (SciDAC) program under Award No. KC-030106062653. S.G. also acknowledges a doctoral dissertation fellowship from the University of Minnesota. The research also benefitted from computational resources provided by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota and EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle Memorial Institute for the United States Department of Energy under DOE Contract No. DE-AC05-76RL1830. There are no conflicts to declare. Publisher Copyright: {\textcopyright} 2019 Author(s).",

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AU - Govind, Niranjan

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N2 - 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.

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

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