TY - JOUR
T1 - From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again
T2 - A Tale of Variational Energy Decomposition Analysis
AU - Mao, Yuezhi
AU - Loipersberger, Matthias
AU - Horn, Paul R.
AU - Das, Akshaya
AU - Demerdash, Omar
AU - Levine, Daniel S.
AU - Prasad Veccham, Srimukh
AU - Head-Gordon, Teresa
AU - Head-Gordon, Martin
N1 - Publisher Copyright:
© 2020 Annual Reviews Inc.. All rights reserved.
PY - 2020/4/20
Y1 - 2020/4/20
N2 - 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, N binf? einf? 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.
AB - 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, N binf? einf? 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.
UR - http://www.scopus.com/inward/record.url?scp=85104498331&partnerID=8YFLogxK
U2 - 10.1146/annurev-physchem-090419-115149
DO - 10.1146/annurev-physchem-090419-115149
M3 - Review article
C2 - 33636998
AN - SCOPUS:85104498331
SN - 0066-426X
VL - 72
SP - 641
EP - 666
JO - Annual Review of Physical Chemistry
JF - Annual Review of Physical Chemistry
ER -