A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation

Abstract

AbstractsA new method is proposed for the analysis of components of molecular interaction energy within the Hartree-Fock approximation. The liartree-Fock molecular orbitals of the isolated molecules are used as the basis for the construction of Fock matrix of the supermolecule. Then certain blocks of this matrix are set to zero subject to specify boundary conditions of the supermolecule molecular orbitals, and the resultant matrix is diagonalized iteratively to obtain the desired energy components. This method can be considered as an extension of our previous method, but has an advantage in the explicit definition of the charge transfer energy, placing it on an equal footing with the exchange and polarization terms. The new method is compared with existing perturbation methods, and is also applied to the energy and electron density decomposition of (H,O),.On propose une nouvelle mkthode pour analyser les composantes de I'energie d'interaction moliculaire dans le cadre de I'approximation Hartree-Fock. Les orbitales moleculaires des molkcules isolkes sont utiliskes comme base pour construire la matrice de Fock de la supermolecule. Certains blocs de cette matrice sont mis egaux a zero selon des conditions aux limites spkcifiques et la matrice rksultante est diagonalisee d'une faqon iterative pour obtenir les composantes cherchkes. Cette mkthode-ci peut itre considerke comme une extension de notre mkthode antkrieure mais elle a un avantage dans la definition explicite de I'energie de transfert de charge, qui est mise ici au mime rang que les termes d'kchange et de polarisation. La nouvelle mkthode est comparke aux methodes de perturbation traditionelles. Elle a dtk appliquee a la decomposition de I'energie et de la densite ilectronique de (H20)2.Es wird eine neue Methode fur die Analyse der Komponenten der molekularen Wechselwirkungsenergie in der Hartree-Fock-Naherung vorgeschlagen. Die Hartree-FockOrbitale der freien Molekiile werden verwendet als Basis fur die Konstruktion der Fock' schen Matrix des Supermolekiils. Gewisse Blocke dieser Matrix werden nach spezifischen Grenzbedingungen gleich Null gesetzt, und die resultierende Matrix wird in einer iterativen Weise diagonalisiert um die gewiinschten Energiekomponenten zu geben. Diese Methode kann als eine Ergazung unserer friiheren Methode betrachtet werden. Sie hat aber einen Vorteil in der expliziten Definition der Ladungsuberfuhrungsenergie, die hier an denselben Niveau wie die Austausch-und Polarisationsglieder hingestellt wird. Die neue Methode wird mit existierenden Storungsmethoden verglichen. Sie wird auf die Zerlegung der Energie und der Elektronendichte von (H20), angewandt.

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

“…Natural bond orbital (NBO) 75 and natural EDA 38 suggests that CT is predominant 39,40,76 because if CT is neglected, NBO analysis shows no binding at the water dimer equilibrium geometry. However, other earlier decomposition methods [33][34][35][36][37] estimated that CT contributes only around 20% of the overall binding energy 34,35,77 .…”

“…• Unlike earlier decomposition methods [33][34][35][36][37][38][39][40] , ALMO EDA and CTA treat the polarization term in a variationally optimal way. Therefore, CT effects (i.e.…”

Pair interaction energy decomposition analysis

“…As expected from the physical model, DE PL0 , DE PLÁPL and DE ES0 are exactly the same in EDA and PIEDA (DE ES0 values agree because the electrostatic interaction is pairwise in nature, so that dimer calculations take all of it into account). Other quantities have a certain amount of higher body terms and thus there is some small dis-crepancy observed, except for (H 2 O) 2 , in which case the agreement for all terms is perfect.…”

“…2 Their energy decomposition approach (EDA, also called sometimes the KM analysis) has become standard [3][4][5] and has been widely used during the 30 years since its appearance. [6][7][8] It also served as a basis to a great number of further improvements and development.…”

Possibility of Hydrogen Bonding Between Molecules of Pentyl Ester of p-(N-α-D-Glucopyranoside)Aminobenzoic Acid

“…Расчеты энергии взаимодействия в иссле-дуемых молекулярных системах и ее декомпо-зиция были проведены по методу Морокумы [13,14] (HF/6-31G (PC GAMESS) [12]). …”