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

Loipersberger, Matthias; Lee, Joonho; Mao, Yuezhi; Das, Akshaya K.; Ikeda, Kevin; Thirman, Jonathan; Head-Gordon, Teresa; Head-Gordon, Martin

doi:10.1021/acs.jpca.9b08586

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

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:

Loipersberger, Matthias ^[1];

^[1];

^[1]; Das, Akshaya K. ^[1]; Ikeda, Kevin ^[1]; Thirman, Jonathan ^[1];

^[2];

^[1]

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:: Mon Oct 07 00:00:00 EDT 2019

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.

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                    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

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                    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.

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@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}

}

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Figure 1: A representation for each of the three types of double excitations for a two-fragment system (A and B): on fragment (type I), charge conserving (type II) and charge transferring (III). In the case of RMP2 single excitations are also included, for which the on fragment and charge conservingmore »

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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

Abstract

Citation Formats

Figures / Tables:

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