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

Abstract

We describe a new approach to extract information about an excited state wave function using a reduced orbital space molecular orbital (MO) 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 INDO/S method 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 (ESA) spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine (ZnPc), and nickel TPyP using a semiempirical Hamiltonian.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Supercomputing Inst.
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Contributing Org.:
Minnesota Supercomputing Institute (MSI)
OSTI Identifier:
1507019
Alternate Identifier(s):
OSTI ID: 1515848
Report Number(s):
PNNL-SA-135100
Journal ID: ISSN 0021-9606; KC-030106062653
Grant/Contract Number:  
SC0008688; FG02-17ER16362; AC05-76RL1830; AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 10; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ghosh, Soumen, Asher, Jason C., Gagliardi, Laura, Cramer, Christopher J., and Govind, Niranjan. A semiempirical effective Hamiltonian based approach for analyzing excited state wave functions and computing excited state absorption spectra using real-time dynamics. United States: N. p., 2019. Web. doi:10.1063/1.5061746.
Ghosh, Soumen, Asher, Jason C., Gagliardi, Laura, Cramer, Christopher J., & Govind, Niranjan. A semiempirical effective Hamiltonian based approach for analyzing excited state wave functions and computing excited state absorption spectra using real-time dynamics. United States. doi:10.1063/1.5061746.
Ghosh, Soumen, Asher, Jason C., Gagliardi, Laura, Cramer, Christopher J., and Govind, Niranjan. Thu . "A semiempirical effective Hamiltonian based approach for analyzing excited state wave functions and computing excited state absorption spectra using real-time dynamics". United States. doi:10.1063/1.5061746.
@article{osti_1507019,
title = {A semiempirical effective Hamiltonian based approach for analyzing excited state wave functions and computing excited state absorption spectra using real-time dynamics},
author = {Ghosh, Soumen and Asher, Jason C. and Gagliardi, Laura and Cramer, Christopher J. and Govind, Niranjan},
abstractNote = {We describe a new approach to extract information about an excited state wave function using a reduced orbital space molecular orbital (MO) 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 INDO/S method 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 (ESA) spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine (ZnPc), and nickel TPyP using a semiempirical Hamiltonian.},
doi = {10.1063/1.5061746},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 150,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
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Works referenced in this record:

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018