Energy decomposition analysis of covalent bonds and intermolecular interactions

Abstract

An energy decomposition analysis method is implemented for the analysis of both covalent bonds and intermolecular interactions on the basis of single-determinant Hartree-Fock ͑HF͒ ͑restricted closed shell HF, restricted open shell HF, and unrestricted open shell HF͒ wavefunctions and their density functional theory analogs. For HF methods, the total interaction energy from a supermolecule calculation is decomposed into electrostatic, exchange, repulsion, and polarization terms. Dispersion energy is obtained from second-order Møller-Plesset perturbation theory and coupled-cluster methods such as CCSD and CCSD͑T͒. Similar to the HF methods, Kohn-Sham density functional interaction energy is decomposed into electrostatic, exchange, repulsion, polarization, and dispersion terms. Tests on various systems show that this algorithm is simple and robust. Insights are provided by the energy decomposition analysis into H 2 , methane C-H, and ethane C-C covalent bond formation, CH 3 CH 3 internal rotation barrier, water, ammonia, ammonium, and hydrogen fluoride hydrogen bonding, van der Waals interaction, DNA base pair formation, BH 3 NH 3 and BH 3 CO coordinate bond formation, Cu-ligand interactions, as well as LiF, LiCl, NaF, and NaCl ionic interactions.

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

“…An alternative approach to separate the exchange and Coulomb contributions is using a DFT wavefunction in which the definition of exchange follows naturally from the exchange component of the density functional, as is done in LMO-EDA, 33 GKS-EDA, 34 and steric-based EDA 35 and a procedure involving projection operators introduced by Head-Gordon and co-workers. 36 A.…”

Electronic structure theory to decipher the chemical bonding in actinide systems

“…These developments have taken place aiming to overcome limitations of the original schemes and provide more chemical significance to the energy components, which are not uniquely defined. We can cite, for example, CSOV (Constrained Space Orbital Variations) [107], RVS (Reduced Variational Space Self-Consistent-Field) [108], SAPT (Symmetry-Adapted Perturbation Theory) [109], NEDA (Natural Energy Decomposition Analysis) [110][111][112], LMOEDA (Localized Molecular Orbital Energy Decomposition Analysis) [113], ALMO-EDA (Absolutely Localized Molecular Orbital [114]), FMO (Fragment Molecular Orbital [115][116][117]) and a Morokuma-type EDA developed by Ziegler and Rauk [118][119][120]. Certainly, this list is not exhaustive, but recalls some popular currently used EDA schemes.…”

“…Therefore, an usable method is not always accessible, each method having well defined application domains. As an illustration, the localised molecular orbital LMOEDA scheme of Su and Li [113] is implemented for the analysis of both covalent bonds and intermolecular interactions on the basis of single-determinant HF (restricted closed shell HF, restricted open shell HF, and unrestricted open shell HF) wave functions and their DFT equivalents. For HF methods, the total interaction energy is decomposed into electrostatic, exchange, repulsion, and polarisation terms.…”

Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals for Large-Scale Density Functional Theory Calculations in Drug Design

“…The components of this frozen energy decomposition are formally similar to the components described in the LMO EDA 16 but with inclusion of a new component ∆E CORR that isolates the correlation energy change on orthogonalisation contained within the LMO EDA 'polarisation' term.…”

“…30 These methods have demonstrated varying degrees of success in the study of protein-ligand interactions, 31 and show that the problem of separating polarisation and charge transfer effects is approached in a variety of ways. For example, schemes such as the localised molecular orbital (LMO) 16 and extended transition state (ETS) [32][33][34][35] EDAs simply do not seek to separate polarisation and charge transfer effects at all. Other schemes that attempt this partitioning consider the problem as involving the optimisation of molecular orbitals (MOs) subject to conditions that impose localisation to particular fragments.…”