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Title: Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts

Abstract

Accurate and rapid quantum mechanical prediction of solvatochromic shifts, particularly in systems where charge transfer plays a significant role, is important for many aspects of molecular and material design. Although the semiempirical INDO/SCI approach is computationally efficient and performs well for charge-transfer states, the availability of implicit solvent approaches has been limited. As such, we implement the COSMO solvent model with a perturbative state-specific correction to the excited-state energies with the INDO/SCI method. We show that for a series of prototypical π-conjugated molecules, our newly implemented INDO/SCI/COSMO model yields more accurate absorption energies and comparably accurate solvatochromic shifts to those computed using TD-ωB97XD and CIS with COSMO solvation at a substantially lower computational cost.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1594590
Grant/Contract Number:  
SC0004752; FG02- 10ER16153
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 49; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Solvents; Energy; Absorption Molecules

Citation Formats

Gieseking, Rebecca L., Ratner, Mark A., and Schatz, George C. Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b10487.
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Gieseking, Rebecca L., Ratner, Mark A., & Schatz, George C. Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts. United States. https://doi.org/10.1021/acs.jpca.6b10487
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Gieseking, Rebecca L., Ratner, Mark A., and Schatz, George C. Tue . "Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts". United States. https://doi.org/10.1021/acs.jpca.6b10487. https://www.osti.gov/servlets/purl/1594590.
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@article{osti_1594590,
title = {Implementation of INDO/SCI with COSMO Implicit Solvation and Benchmarking for Solvatochromic Shifts},
author = {Gieseking, Rebecca L. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {Accurate and rapid quantum mechanical prediction of solvatochromic shifts, particularly in systems where charge transfer plays a significant role, is important for many aspects of molecular and material design. Although the semiempirical INDO/SCI approach is computationally efficient and performs well for charge-transfer states, the availability of implicit solvent approaches has been limited. As such, we implement the COSMO solvent model with a perturbative state-specific correction to the excited-state energies with the INDO/SCI method. We show that for a series of prototypical π-conjugated molecules, our newly implemented INDO/SCI/COSMO model yields more accurate absorption energies and comparably accurate solvatochromic shifts to those computed using TD-ωB97XD and CIS with COSMO solvation at a substantially lower computational cost.},
doi = {10.1021/acs.jpca.6b10487},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 49,
volume = 120,
place = {United States},
year = {Tue Dec 06 00:00:00 EST 2016},
month = {Tue Dec 06 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acs.jpca.6b10487
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