Natural population analysis

Abstract

A method of ‘‘natural population analysis’’ has been developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis sets. The natural analysis is an alternative to conventional Mulliken population analysis, and seems to exhibit improved numerical stability and to better describe the electron distribution in compounds of high ionic character, such as those containing metal atoms. We calculated ab initio SCF-MO wave functions for compounds of type CH3X and LiX (X=F, OH, NH2, CH3, BH2, BeH, Li, H) in a variety of basis sets to illustrate the generality of the method, and to compare the natural populations with results of Mulliken analysis, density integration, and empirical measures of ionic character. Natural populations are found to give a satisfactory description of these molecules, providing a unified treatment of covalent and extreme ionic limits at modest computational cost.

Keywords

Ionic bondingMulliken population analysisGeneralityPopulationComputational chemistryWave functionMolecular orbitalIonic potentialCovalent bondAb initioBasis (linear algebra)Atomic orbitalChemistryChemical physicsStatistical physicsMoleculeAtomic physicsPhysicsDensity functional theoryElectronMathematicsQuantum mechanicsIonGeometryOrganic chemistry

Affiliated Institutions

University of Wisconsin–Madison US

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Publication Info

Year: 1985
Type: article
Volume: 83
Issue: 2
Pages: 735-746
Citations: 9571
Access: Closed

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APA Style

                            
                                    Alan E. Reed, 
                                
                                    Robert B. Weinstock, 
                                
                                    Frank Weinhold
                                
                            (1985). 
                            Natural population analysis. 
                            The Journal of Chemical Physics
                            , 83
                            (2)
                            , 735-746.
                            https://doi.org/10.1063/1.449486

Identifiers

DOI: 10.1063/1.449486