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

Ghosh, Soumen; Asher, Jason C.; Gagliardi, Laura; Cramer, Christopher J.; Govind, Niranjan

doi:10.1063/1.5061746

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

Journal Article · Thu Mar 14 00:00:00 EDT 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5061746· OSTI ID:1507019

^[1]; Asher, Jason C. ^[1];

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Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Supercomputing Inst.
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

We describe a new orbital space molecular orbital (MO) decomposition approach to analyze real-time spectra. 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 the UV/vis spectrum of f-coronene. We also compare the convergence of conventional fast Fourier transformation with the recently proposed Padé appoximants approach of Bruner et al. (A. Bruner, D. LaMaster, K. Lopata, J. Chem. Theory ComputWe 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 the first excited state absorption spectra of coronene, 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP), zinc phthalocyanine (ZnPc), and nickel TPyP, this being a first study applying a semiempirical Hamiltonian to the computation of first excited state absorption spectra.. 2016, 12, 3741–3750) for MO pair spectra. Finally, two different approaches to choose the reduced orbital space are compared. Our approach provides a simplified and efficient means to analyze real-time spectra irrespective of the nature of the excitations.

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Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Contributing Organization:: Minnesota Supercomputing Institute (MSI)

Grant/Contract Number:: SC0008688; FG02-17ER16362; AC05-76RL1830; AC05-76RL01830

OSTI ID:: 1507019

Alternate ID(s):: OSTI ID: 1515848

Report Number(s):: PNNL-SA-135100; KC-030106062653

Journal Information:: Journal of Chemical Physics, Vol. 150, Issue 10; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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References (54)

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