Energy Decomposition Scheme Based on the Generalized Kohn–Sham Scheme

Abstract

In this paper, a new energy decomposition analysis scheme based on the generalized Kohn-Sham (GKS) and the localized molecular orbital energy decomposition analysis (LMO-EDA) scheme, named GKS-EDA, is proposed. The GKS-EDA scheme has a wide range of DFT functional adaptability compared to LMO-EDA. In the GKS-EDA scheme, the exchange, repulsion, and polarization terms are determined by DFT orbitals; the correlation term is defined as the difference of the GKS correlation energy from monomers to supermolecule. Using the new definition, the GKS-EDA scheme avoids the error of LMO-EDA which comes from the separated treatment of EX and EC functionals. The scheme can perform analysis both in the gas and in the condensed phases with most of the popular DFT functionals, including LDA, GGA, meta-GGA, hybrid GGA/meta-GGA, double hybrid, range-separated (long-range correction), and dispersion correction. By the GKS-EDA scheme, the DFT functionals assessment for hydrogen bonding, vdW interaction, symmetric radical cation, charge-transfer, and metal-ligand interaction is performed.

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.…”

“…Interaction energy contributions in a T-shaped benzene dimer in kcal/mol. 34,58 The interaction is dominated by dispersion that counteracts Pauli repulsion (EX in SAPT and EX + REP in GKS-EDA). GKS-EDA predicts larger electrostatic (ELST) and polarization (POL) contributions than SAPT.…”

“…34,91 Both in SAPT and GKS-EDA picture, the interaction is driven by the electrostatic (ELST) and dipole-dipole (IND and POL) interactions with only a small contribution from dispersion. The correlation term in GKS-EDA is indicated by (CORR).…”

An energy decomposition analysis study for intramolecular non-covalent interaction

“…An EDA method that is able to perform interaction analysis for open-shell system with RO (restricted-open) or U (unrestricted) type orbitals can be used. In this work, the generalized Kohn-Sham based energy decomposition analysis scheme, GKS-EDA [25] is employed for the decomposition analysis. It is developed based on LMO-EDA [26], dividing the total interaction into electrostatic, exchange, repulsion, polarization, correlation and dispersion etc.…”

Communication: Physical origins of ionization potential shifts in mixed carboxylic acids and water complexes

“…In phenol and indole complexes with water, the IP values are shifted to the red by −13.15 kcal/mol and −9.03 kcal/mol, respectively. 19,20 Generalized KohnSham energy decomposition analysis (GKS-EDA) 21 promises an understanding of the physical origins leading to the contrasting IP shifts in mixed carboxylic acids and water dimers, specifically 9HFCA-HCOOH and 9HFCA-H 2 O. Applying GKS-EDA to 9HFCA-HCOOH dimer leads to surprising results, quite different from the more common concepts, as found for 9HFCA-H 2 O.…”