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Title: Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals

An energy decomposition analysis (EDA) scheme is developed for understanding the intermolecular interaction involving molecules in their excited states. The EDA utilizes absolutely localized molecular orbitals to define intermediate states and is compatible with excited state methods based on linear response theory such as configuration interaction singles and time-dependent density functional theory. The shift in excitation energy when an excited molecule interacts with the environment is decomposed into frozen, polarization, and charge transfer contributions, and the frozen term can be further separated into Pauli repulsion and electrostatics. These terms can then be added to their counterparts obtained from the ground state EDA to form a decomposition of the total interaction energy. The EDA scheme is applied to study a variety of systems, including some model systems to demonstrate the correct behavior of all the proposed energy components as well as more realistic systems such as hydrogen-bonding complexes (e.g., formamide-water, pyridine/pyrimidine-water) and halide (F -,Cl -)-water clusters that involve charge-transfer-to-solvent excitations.
Authors:
 [1] ;  [2] ; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry and Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Science Division
  2. Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry and Dept. of Chemistry
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 6; Related Information: © 2018 Author(s).; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; hydrogen bonding; intermolecular forces; excitation energies; Doppler effect; self consistent field methods; configuration interaction; time dependent density functional theory; chemical compounds; electrostatics
OSTI Identifier:
1434021
Alternate Identifier(s):
OSTI ID: 1420021

Ge, Qinghui, Mao, Yuezhi, and Head-Gordon, Martin. Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals. United States: N. p., Web. doi:10.1063/1.5017510.
Ge, Qinghui, Mao, Yuezhi, & Head-Gordon, Martin. Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals. United States. doi:10.1063/1.5017510.
Ge, Qinghui, Mao, Yuezhi, and Head-Gordon, Martin. 2018. "Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals". United States. doi:10.1063/1.5017510.
@article{osti_1434021,
title = {Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals},
author = {Ge, Qinghui and Mao, Yuezhi and Head-Gordon, Martin},
abstractNote = {An energy decomposition analysis (EDA) scheme is developed for understanding the intermolecular interaction involving molecules in their excited states. The EDA utilizes absolutely localized molecular orbitals to define intermediate states and is compatible with excited state methods based on linear response theory such as configuration interaction singles and time-dependent density functional theory. The shift in excitation energy when an excited molecule interacts with the environment is decomposed into frozen, polarization, and charge transfer contributions, and the frozen term can be further separated into Pauli repulsion and electrostatics. These terms can then be added to their counterparts obtained from the ground state EDA to form a decomposition of the total interaction energy. The EDA scheme is applied to study a variety of systems, including some model systems to demonstrate the correct behavior of all the proposed energy components as well as more realistic systems such as hydrogen-bonding complexes (e.g., formamide-water, pyridine/pyrimidine-water) and halide (F-,Cl-)-water clusters that involve charge-transfer-to-solvent excitations.},
doi = {10.1063/1.5017510},
journal = {Journal of Chemical Physics},
number = 6,
volume = 148,
place = {United States},
year = {2018},
month = {2}
}