Variational determination of the zero-flux surfaces of atoms in molecules
- 1 March 1995
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 84 (4), 707-716
- https://doi.org/10.1080/00268979500100481
Abstract
A functional minimized by functions representing zero-flux surface sheets in curvilinear coordinates is proposed. A discrete version of this functional serves as the basis for a new variational approach to the determination of the zero-flux surfaces of atoms in molecules. Analytical expressions for the zero-flux surface sheets are obtained by solving a system of nonlinear equations for variational parameters of a trial function. The new method, which is computationally inexpensive, produces atomic surfaces that are 10–100 times more accurate than those afforded by the previously published algorithms. Results of numerical tests demonstrate that, when used in conjunction with an adaptive quadrature scheme, these surfaces yield atomic charges with errors smaller than 3 × 10-5 per atom. The numerous advantages of analytical representations for the atomic zero-flux surfaces are discussed.Keywords
This publication has 15 references indexed in Scilit:
- A new robust algorithm for fully automated determination of attractor interaction lines in moleculesChemical Physics Letters, 1994
- Similarity of atoms in moleculesJournal of the American Chemical Society, 1993
- Rigorous interpretation of electronic wave functions. 2. Electronic structures of selected phosphorus, sulfur, and chlorine fluorides and oxidesInorganic Chemistry, 1993
- Rapid evaluation of atomic properties with mixed analytical/numerical integrationChemical Physics Letters, 1993
- Electronegativities in situ, bond hardnesses, and charge-transfer components of bond energies from the topological theory of atoms in moleculesJournal of the American Chemical Society, 1993
- An efficient evaluation of atomic properties using a vectorized numerical integration with dynamic thresholdingChemical Physics Letters, 1992
- Topological properties of electron density in search of steric interactions in molecules: electronic structure calculations on ortho-substituted biphenylsJournal of the American Chemical Society, 1992
- An observable-based interpretation of electronic wavefunctions: application to “hypervalent” moleculesJournal of Molecular Structure: THEOCHEM, 1992
- Covalent bond orders in the topological theory of atoms in moleculesJournal of the American Chemical Society, 1991
- Calculation of the average properties of atoms in moleculesJournal of Physics B: Atomic and Molecular Physics, 1981