Virial Partitioning of Charge Distributions and Properties of Diatomic Hydrides; NaH ↔ HCl

Abstract

. Can. J. Chem. 52, 2268Chem. 52, (1974 The virial partitioning method is applied to the ground states of the AH diatomic hydrides (A = Na, Mg, Al, Si, P, S, C1) in their neutral and charged forms. This is a spatial partitioning of a molecular system, the partitioning surfaces, which in this instance divide each molecule into an (A) and an (H) fragment, bcing determined by the topographical features of the electronic charge distribution. The kinetic and potential energies of the virial fragments are well-defined quantities and in addition, satisfy the quantum mechanical virial relationship. Most important, virial fragments faithfully reflect the chemistry of the individual elemental components of molecular systems, the fragments and their properties remaining nearly constant or changing when in different systems, in accordance with chemical expectations.The populations of (H) in combination with (A) are used to order the first-and second-row elements (neutral and charged) in their abilities to abstract or donate charge relative to hydrogen. This ordering is of general interest as the population of (H) in A H changes little on passage to the general (most stable) polyatomic AH,,. The virial equations are used to relate the kinetic energy of binding in AH to the changes in the potential energies and total energies of each fragment. One finds, in comparison of first-and second-row results, that the nature of the most important stabilizing interactions in the formation of AH change in a similar manner across the two rows of elements, but the change in the second-row set occurs two members to the right with respect to the first-row set.R. F. W. BADER et R. R. MESSER. Can. J. Chem. 52, 2268Chem. 52, (1974 On applique la methode de partition virielle aux formes neutres et chargtes des Ctats fondamentaux des hydrures diatomiques AH (A = Na, Mg, Al, Si, P, S, C1). C'est une partition spatiale d'un systeme moleculaire, la partition de surfaces, qui dans cette circonstance divise chaque molecule en un fragment (A) et un fragment (H), determines par les caracthes topographiques de la distribution de la charge electroniq?le. Les energies cinetiques et potentielles des fragments viriels sont des quantitis bien definies et de plus satisfont la micanique quantique virielie. Plus jmportant encore, les fragments viriels refletent fidelement la chimie des composants elementaires individuels des systemes moleculaires, les fragments et leurs propriktes restent presque constants ou changent avec les diffkrents systemes conformement aux previsions chimiques.On utilise ies populations de (H) en combinaison avec (A) pour classer les eltments de la premiere et de la deuxieme rangee (neutres et charges) selon leur habilitt par rapport a l'hydrogene d'arracher ou donner la charge. Ce classenlent est d'un interet general sachant que la population de (H) dans A H change peu lorsque I'on passe au produit polyatomique general (plus stable) AH,,. On utilise les equations virielles pour etablir un rapport entre I'energie cinitique de liaison...

Charge transfer and three-centre bonding in monoprotonated and diprotonated 2,2'-bipyridylium decahydro-closo-decaborate(2–)

“…Other methods for estimating atomic charges applied to boron clusters and similar species include the refinement of electron populations in density basis sets and radial integration of the total density out to a fixed radius or surface (Ito & Higashi, 1983;Bader & Messer, 1974). The former technique provides information relevant to postulated sets of orbitals but frequently overestimates atomic charges.…”

Atomic Charges and Electron Density Partitioning

“…The first is due to Bader and coworkers (Bader andBeddall 1972, 1973;Bader and Messer 1974) and the second to Hirshfeld (1977). We briefly describe each of these schemes and then compare the charges derived from near Hartree-Fock limit diatomic wavefunctions by both schemes.…”

“…ionicity and acidity), as is evident from the analyses of diatomic molecules by , , Bader and Messer (1974), and of aliphatic alcohols and amines by Stutchbury and Cooper (1983). The fact that typical electron populations for the fragments are usually quite different from those of neutral atoms has received limited attention so far.…”

QTAIM in Drug Discovery and Protein Modeling

“…This is the boundary condition necessary for application of Schwinger's principle of stationary action to an open system [49]. An extensive body of work [16][17][18][19][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63] has revealed that virial partitioning gives a natural and rigorous meaning to the intuitive concept of an atom in a molecule, and convergence of the electrostatic interaction based on topological atoms has been computationally demonstrated [64][65][66]. An extensive body of work [16][17][18][19][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63] has revealed that virial partitioning gives a natural and rigorous meaning to the intuitive concept of an atom in a molecule, and convergence of the electrostatic interaction based on topological atoms has been computationally demonstrated [64][65][66].…”