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 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 excitedmore » 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.« less

Authors:

Ghosh, Soumen  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-0850-4855"

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

• Search DOE PAGES for author "Gagliardi, Laura"
• Search DOE PAGES for ORCID "0000-0001-5227-1396"

Cramer, Christopher J.  ^[1];

• Search DOE PAGES for author "Cramer, Christopher J."
• Search DOE PAGES for ORCID "0000-0001-5048-1859"

Govind, Niranjan  ^[2]

• Search DOE PAGES for author "Govind, Niranjan"
• Search DOE PAGES for ORCID "0000-0003-3625-366X"

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+ Show Author Affiliations

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:

Thu Mar 14 00:00:00 EDT 2019

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). Chemical Sciences, Geosciences, and Biosciences Division

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:

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