An energy decomposition analysis for intermolecular interactions from an absolutely localized molecular orbital reference at the coupled-cluster singles and doubles level

Azar, R. Julian; Head-Gordon, Martin

doi:doi:10.1063/1.3674992

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Coarse-grained potential models for structural prediction of carbon dioxide (CO₂) in confined environments

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We propose a wave function-based method for the decomposition of intermolecular interaction energies into chemically-intuitive components, isolating both mean-field- and explicit correlation-level contributions. We begin by solving the locally-projected self-consistent field for molecular interactions equations for a molecular complex, obtaining an intramolecularly polarized reference of self-consistently optimized, absolutely-localized molecular orbitals (ALMOs), determined with the constraint that each fragment MO be composed only of atomic basis functions belonging to its own fragment. As explicit inter-electronic correlation is integral to an accurate description of weak forces underlying intermolecular interaction potentials, namely, coordinated fluctuations in weakly interacting electronic densities, we add dynamical correlation to the ALMO polarized reference at the coupled-cluster singles and doubles level, accounting for explicit dispersion and charge-transfer effects, which map naturally onto the cluster operator. We demonstrate the stability of energy components with basis set extension, follow the hydrogen bond-breaking coordinate in the C_s-symmetry water dimer, decompose the interaction energies of dispersion-bound rare gas dimers and other van der Waals complexes, and examine charge transfer-dominated donor-acceptor interactions in borane adducts. We compare our results with high-level calculations and experiment when possible.

Article Outline

INTRODUCTION
THEORY
1. Subspaces and strong orthonormality
2. Coupled-cluster EDA
RESULTS
1. Water dimer
2. Rare gas and other dispersion-bound complexes
3. Charge transfer-dominated borane adducts
DISCUSSION AND FUTURE DIRECTION

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KEYWORDS and PACS

Keywords

charge exchange, coupled cluster calculations, decomposition, fluctuations, hydrogen bonds, organic compounds, potential energy functions, SCF calculations, van der Waals forces, water, wave functions

PACS

31.15.bw

Coupled-cluster theory
31.15.xr

Self-consistent-field methods
34.20.Cf

Interatomic potentials and forces
82.30.Fi

Ion-molecule, ion-ion, and charge-transfer reactions
34.70.+e

Charge transfer
82.30.Lp

Decomposition reactions (pyrolysis, dissociation, and fragmentation)

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3674992

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

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