The development of post-Hartree-Fock (post-HF) energy decomposition schemes that are able to decompose the HF and correlation components of the interaction energy into chemically meaningful contributions is a very active field of research. One of the challenges is to provide a clear-cut quantification to the elusive London dispersion component of the intermolecular interaction. London dispersion is well-known to be a pure correlation effect, and as such it is not properly described by mean field theories. In this context, we have recently developed the local energy decomposition (LED) analysis, which provides a chemically meaningful decomposition of the interaction energy between two or more fragments computed at the domain-based local pair natural orbitals coupled cluster (DLPNO-CCSD(T)) level of theory. In this work, this scheme is used in conjunction with other interpretation tools to study a series of molecular adducts held together by intermolecular interactions of different natures. The HF and correlation components of the interaction energy are thus decomposed into a series of chemically meaningful contributions. Emphasis is placed on discussing the physical effects associated with the inclusion of electron correlation. It is found that four distinct physical effects can contribute to the magnitude of the correlation part of intermolecular binding energies (Eint C ): (i) London dispersion, (ii) the correlation correction to the reference induction energy, (iii) the correlation correction to the electron sharing process, and (iv) the correlation correction to the permanent electrostatics. As expected, the largest contribution to the correlation binding energy of neutral, apolar molecules is London dispersion, as in the argon dimer case. In contrast, the correction for the HF induction energy dominates Eint C in systems in which an apolar molecule interacts with charged or strongly polar species, as in Ar-Li + . This effect has its origin in the systematic underestimation of polarizabilities at the HF level of theory. For similar reasons, electron sharing largely contributes to the correlation binding energy of covalently bound molecules, as in the beryllium dimer case. Finally, the correction for HF permanent electrostatics significantly contributes to Eint C in molecules with strong dipoles, such as water and hydrogen fluoride dimers. This effect originates from the characteristic overestimation of dipole moments at the HF level of theory, leading in some cases to positive Eint C values. Our results are apparently in contrast to the widely accepted view that Eint C is typically dominated by London dispersion, at least, in the strongly interacting region. Clearly, post-HF energy decomposition schemes are very powerful tools to analyze, categorize, and understand the various contributions to the intermolecular interaction energy. Hopefully, this will eventually lead to insights that are helpful in designing systems with tailored properties. All analysis tools presented in this work will be available free of charge in the next release of the ORCA program package.

### Effect of Electron Correlation on Intermolecular Interactions: A Pair Natural Orbitals Coupled Cluster Based Local Energy Decomposition Study

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*Bistoni G.*^{}

^{}

##### 2019

#### Abstract

The development of post-Hartree-Fock (post-HF) energy decomposition schemes that are able to decompose the HF and correlation components of the interaction energy into chemically meaningful contributions is a very active field of research. One of the challenges is to provide a clear-cut quantification to the elusive London dispersion component of the intermolecular interaction. London dispersion is well-known to be a pure correlation effect, and as such it is not properly described by mean field theories. In this context, we have recently developed the local energy decomposition (LED) analysis, which provides a chemically meaningful decomposition of the interaction energy between two or more fragments computed at the domain-based local pair natural orbitals coupled cluster (DLPNO-CCSD(T)) level of theory. In this work, this scheme is used in conjunction with other interpretation tools to study a series of molecular adducts held together by intermolecular interactions of different natures. The HF and correlation components of the interaction energy are thus decomposed into a series of chemically meaningful contributions. Emphasis is placed on discussing the physical effects associated with the inclusion of electron correlation. It is found that four distinct physical effects can contribute to the magnitude of the correlation part of intermolecular binding energies (Eint C ): (i) London dispersion, (ii) the correlation correction to the reference induction energy, (iii) the correlation correction to the electron sharing process, and (iv) the correlation correction to the permanent electrostatics. As expected, the largest contribution to the correlation binding energy of neutral, apolar molecules is London dispersion, as in the argon dimer case. In contrast, the correction for the HF induction energy dominates Eint C in systems in which an apolar molecule interacts with charged or strongly polar species, as in Ar-Li + . This effect has its origin in the systematic underestimation of polarizabilities at the HF level of theory. For similar reasons, electron sharing largely contributes to the correlation binding energy of covalently bound molecules, as in the beryllium dimer case. Finally, the correction for HF permanent electrostatics significantly contributes to Eint C in molecules with strong dipoles, such as water and hydrogen fluoride dimers. This effect originates from the characteristic overestimation of dipole moments at the HF level of theory, leading in some cases to positive Eint C values. Our results are apparently in contrast to the widely accepted view that Eint C is typically dominated by London dispersion, at least, in the strongly interacting region. Clearly, post-HF energy decomposition schemes are very powerful tools to analyze, categorize, and understand the various contributions to the intermolecular interaction energy. Hopefully, this will eventually lead to insights that are helpful in designing systems with tailored properties. All analysis tools presented in this work will be available free of charge in the next release of the ORCA program package.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.