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Title: Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route

Abstract

Here, we present a reliable and cost-effective procedure for the inclusion of anharmonic effects in excited-state energies and spectroscopic intensities by means of second-order vibrational perturbation theory. This development is made possible thanks to a recent efficient implementation of excited-state analytic Hessians and properties within the time-dependent density functional theory framework. As illustrated in this work, by taking advantage of such algorithmic developments, it is possible to perform calculations of excited-state infrared spectra of medium-large isolated molecular systems, with anharmonicity effects included in both the energy and property surfaces. We also explore the use of this procedure for the inclusion of anharmonic effects in the simulation of vibronic bandshapes of electronic spectra, and compare the results with previous, more approximate models.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [3];  [4];  [4]; ORCiD logo [2];  [1]
  1. Scuola Normale Superiore (SNS), Pisa (Italy)
  2. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
  3. UOS of Pisa (Italy). Inst. of Chemistry of Organometallic Compounds and Italian National Research Council (ICCOM-CNR)
  4. Gaussian, Inc., Wallingford, CT (United States)
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE; European Research Council (ERC); Ministry of Education, Universities and Research (MIUR) (Italy); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1463086
Alternate Identifier(s):
OSTI ID: 1594479
Grant/Contract Number:  
SC0006863; 320951; 20129ZFHFE; XBZ5YA; F59J3R; CHE-1565520
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 6; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Egidi, Franco, Williams-Young, David B., Baiardi, Alberto, Bloino, Julien, Scalmani, Giovanni, Frisch, Michael J., Li, Xiaosong, and Barone, Vincenzo. Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00218.
Egidi, Franco, Williams-Young, David B., Baiardi, Alberto, Bloino, Julien, Scalmani, Giovanni, Frisch, Michael J., Li, Xiaosong, & Barone, Vincenzo. Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route. United States. doi:10.1021/acs.jctc.7b00218.
Egidi, Franco, Williams-Young, David B., Baiardi, Alberto, Bloino, Julien, Scalmani, Giovanni, Frisch, Michael J., Li, Xiaosong, and Barone, Vincenzo. Fri . "Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route". United States. doi:10.1021/acs.jctc.7b00218. https://www.osti.gov/servlets/purl/1463086.
@article{osti_1463086,
title = {Effective Inclusion of Mechanical and Electrical Anharmonicity in Excited Electronic States: VPT2-TDDFT Route},
author = {Egidi, Franco and Williams-Young, David B. and Baiardi, Alberto and Bloino, Julien and Scalmani, Giovanni and Frisch, Michael J. and Li, Xiaosong and Barone, Vincenzo},
abstractNote = {Here, we present a reliable and cost-effective procedure for the inclusion of anharmonic effects in excited-state energies and spectroscopic intensities by means of second-order vibrational perturbation theory. This development is made possible thanks to a recent efficient implementation of excited-state analytic Hessians and properties within the time-dependent density functional theory framework. As illustrated in this work, by taking advantage of such algorithmic developments, it is possible to perform calculations of excited-state infrared spectra of medium-large isolated molecular systems, with anharmonicity effects included in both the energy and property surfaces. We also explore the use of this procedure for the inclusion of anharmonic effects in the simulation of vibronic bandshapes of electronic spectra, and compare the results with previous, more approximate models.},
doi = {10.1021/acs.jctc.7b00218},
journal = {Journal of Chemical Theory and Computation},
number = 6,
volume = 13,
place = {United States},
year = {2017},
month = {4}
}

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Works referencing / citing this record:

Anharmonic excited state frequencies of para -difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives
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  • Tew, David P.; Hättig, Christof; Graf, Nora K.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 26
  • DOI: 10.1039/c8cp06952b

Theoretical studies of atmospheric molecular complexes interacting with NIR to UV light
journal, January 2018

  • Biczysko, Malgorzata; Krupa, Justyna; Wierzejewska, Maria
  • Faraday Discussions, Vol. 212
  • DOI: 10.1039/c8fd00094h