From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

Mao, Yuezhi; Loipersberger, Matthias; Horn, Paul R.; Das, Akshaya; Demerdash, Omar; Levine, Daniel S.; Prasad Veccham, Srimukh; Head-Gordon, Teresa; Head-Gordon, Martin

doi:10.1146/annurev-physchem-090419-115149

Title: From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

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Abstract

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N₂, and BF bound to a [Ru(II)(NH₃)₅]^{2 +} moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

Authors:

Mao, Yuezhi ^[1]; Loipersberger, Matthias ^[1]; Horn, Paul R. ^[1]; Das, Akshaya ^[1]; Demerdash, Omar ^[1]; Levine, Daniel S. ^[1]; Prasad Veccham, Srimukh ^[1]; Head-Gordon, Teresa ^[1]; Head-Gordon, Martin ^[1]

Univ. of California, Berkeley, CA (United States)

Publication Date:: Tue Apr 20 00:00:00 EDT 2021

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1779274

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Annual Review of Physical Chemistry

Additional Journal Information:: Journal Volume: 72; Journal Issue: 1; Journal ID: ISSN 0066-426X

Publisher:: Annual Reviews

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; energy decomposition analysis; intermolecular interactions; hydrogen bonding; dative bonds; radical–molecule complex; force fields

Citation Formats


                    Mao, Yuezhi, Loipersberger, Matthias, Horn, Paul R., Das, Akshaya, Demerdash, Omar, Levine, Daniel S., Prasad Veccham, Srimukh, Head-Gordon, Teresa, and Head-Gordon, Martin. From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis.  United States: N. p., 2021. 
Web.  doi:10.1146/annurev-physchem-090419-115149.

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                    Mao, Yuezhi, Loipersberger, Matthias, Horn, Paul R., Das, Akshaya, Demerdash, Omar, Levine, Daniel S., Prasad Veccham, Srimukh, Head-Gordon, Teresa, & Head-Gordon, Martin. From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis.  United States.  https://doi.org/10.1146/annurev-physchem-090419-115149

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                    Mao, Yuezhi, Loipersberger, Matthias, Horn, Paul R., Das, Akshaya, Demerdash, Omar, Levine, Daniel S., Prasad Veccham, Srimukh, Head-Gordon, Teresa, and Head-Gordon, Martin. Tue .  
"From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis".  United States.  https://doi.org/10.1146/annurev-physchem-090419-115149.  https://www.osti.gov/servlets/purl/1779274.

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@article{osti_1779274,

  title        = {From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis},

  author       = {Mao, Yuezhi and Loipersberger, Matthias and Horn, Paul R. and Das, Akshaya and Demerdash, Omar and Levine, Daniel S. and Prasad Veccham, Srimukh and Head-Gordon, Teresa and Head-Gordon, Martin},

  abstractNote = {Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N2, and BF bound to a [Ru(II)(NH3)5]2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.},

  doi          = {10.1146/annurev-physchem-090419-115149},

  journal      = {Annual Review of Physical Chemistry},

  number       = 1,

  volume       = 72,

  place        = {United States},

  year         = {Tue Apr 20 00:00:00 EDT 2021},

  month        = {Tue Apr 20 00:00:00 EDT 2021}

}

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