Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole
Abstract
To study intermolecular interactions involving radicals at the correlated level, the energy decomposition analysis scheme for second-order Møller-Plesset perturbation theory based on absolutely localized molecular orbitals (ALMO-MP2-EDA) is generalized to unrestricted and restricted open-shell MP2. The benefit of restricted open-shell MP2 is that it can provide accurate binding energies for radical complexes where density functional theory can be error-prone due to delocalization errors. As a model application, the open-shell ALMO-MP2-EDA is applied to study the first solvation step of halogenated benzene radical cations, where both halogen- and hydrogen-bonded isomers are possible. We determine that the lighter halogens favor the hydrogen-bonded form, while the iodine-substituted species prefers halogen bonding due to larger polarizability and charge transfer at the halogen. As a second application, relevant to the activation of CO2 in photoelectrocatalysis, complexes of CO2-· interacting with both pyridine and imidazole are analyzed with ALMO-MP2-EDA. The results reveal the importance of charge transfer into the π* orbital of the heterocycle in controlling the stability of the carbamate binding mode, which is favored for pyridine but not for imidazole.
- Authors:
-
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Dept. of Bioengineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1605260
- Grant/Contract Number:
- AC02-05CH11231; CHE-1665315
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 44; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Loipersberger, Matthias, Lee, Joonho, Mao, Yuezhi, Das, Akshaya K., Ikeda, Kevin, Thirman, Jonathan, Head-Gordon, Teresa, and Head-Gordon, Martin. Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole. United States: N. p., 2019.
Web. doi:10.1021/acs.jpca.9b08586.
Loipersberger, Matthias, Lee, Joonho, Mao, Yuezhi, Das, Akshaya K., Ikeda, Kevin, Thirman, Jonathan, Head-Gordon, Teresa, & Head-Gordon, Martin. Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole. United States. https://doi.org/10.1021/acs.jpca.9b08586
Loipersberger, Matthias, Lee, Joonho, Mao, Yuezhi, Das, Akshaya K., Ikeda, Kevin, Thirman, Jonathan, Head-Gordon, Teresa, and Head-Gordon, Martin. Mon .
"Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole". United States. https://doi.org/10.1021/acs.jpca.9b08586. https://www.osti.gov/servlets/purl/1605260.
@article{osti_1605260,
title = {Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole},
author = {Loipersberger, Matthias and Lee, Joonho and Mao, Yuezhi and Das, Akshaya K. and Ikeda, Kevin and Thirman, Jonathan and Head-Gordon, Teresa and Head-Gordon, Martin},
abstractNote = {To study intermolecular interactions involving radicals at the correlated level, the energy decomposition analysis scheme for second-order Møller-Plesset perturbation theory based on absolutely localized molecular orbitals (ALMO-MP2-EDA) is generalized to unrestricted and restricted open-shell MP2. The benefit of restricted open-shell MP2 is that it can provide accurate binding energies for radical complexes where density functional theory can be error-prone due to delocalization errors. As a model application, the open-shell ALMO-MP2-EDA is applied to study the first solvation step of halogenated benzene radical cations, where both halogen- and hydrogen-bonded isomers are possible. We determine that the lighter halogens favor the hydrogen-bonded form, while the iodine-substituted species prefers halogen bonding due to larger polarizability and charge transfer at the halogen. As a second application, relevant to the activation of CO2 in photoelectrocatalysis, complexes of CO2-· interacting with both pyridine and imidazole are analyzed with ALMO-MP2-EDA. The results reveal the importance of charge transfer into the π* orbital of the heterocycle in controlling the stability of the carbamate binding mode, which is favored for pyridine but not for imidazole.},
doi = {10.1021/acs.jpca.9b08586},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 44,
volume = 123,
place = {United States},
year = {Mon Oct 07 00:00:00 EDT 2019},
month = {Mon Oct 07 00:00:00 EDT 2019}
}
Web of Science
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