{"title":"椭球原子最小基迭代持股人分解。","authors":"Anker M. H. Nielsen, and , Frank Jensen*, ","doi":"10.1021/acs.jctc.5c00788","DOIUrl":null,"url":null,"abstract":"<p >The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic contributions is extended from spherical to ellipsoidal atomic basins. Despite the more flexible parametrization, the derived atomic multipole moments do not systematically improve the reproduction of molecular multipole moments and electrostatic potentials relative to a decomposition into spherical atomic densities. The decomposition can be constrained to exactly reproduce molecular multipole moments, in the present work extended up to hexadecapole moments, and this slightly improves the ability to reproduce the electrostatic potential. A byproduct of the ellipsoidal decomposition is a set of atomic parameters that describe the anisotropic decay of the electron density with distance from the nucleus, and this may be useful in developing anisotropic atomic parameters for use in force fields as well as for defining anisotropic atomic densities for use in quantum crystallography.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"21 18","pages":"8753–8761"},"PeriodicalIF":5.5000,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Minimal Basis Iterative Stockholder Decomposition with Ellipsoidal Atoms\",\"authors\":\"Anker M. H. Nielsen, and , Frank Jensen*, \",\"doi\":\"10.1021/acs.jctc.5c00788\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic contributions is extended from spherical to ellipsoidal atomic basins. Despite the more flexible parametrization, the derived atomic multipole moments do not systematically improve the reproduction of molecular multipole moments and electrostatic potentials relative to a decomposition into spherical atomic densities. The decomposition can be constrained to exactly reproduce molecular multipole moments, in the present work extended up to hexadecapole moments, and this slightly improves the ability to reproduce the electrostatic potential. A byproduct of the ellipsoidal decomposition is a set of atomic parameters that describe the anisotropic decay of the electron density with distance from the nucleus, and this may be useful in developing anisotropic atomic parameters for use in force fields as well as for defining anisotropic atomic densities for use in quantum crystallography.</p>\",\"PeriodicalId\":45,\"journal\":{\"name\":\"Journal of Chemical Theory and Computation\",\"volume\":\"21 18\",\"pages\":\"8753–8761\"},\"PeriodicalIF\":5.5000,\"publicationDate\":\"2025-09-09\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Theory and Computation\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jctc.5c00788\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jctc.5c00788","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Minimal Basis Iterative Stockholder Decomposition with Ellipsoidal Atoms
The minimal basis iterative Stockholder (MBIS) decomposition of molecular electron densities into atomic contributions is extended from spherical to ellipsoidal atomic basins. Despite the more flexible parametrization, the derived atomic multipole moments do not systematically improve the reproduction of molecular multipole moments and electrostatic potentials relative to a decomposition into spherical atomic densities. The decomposition can be constrained to exactly reproduce molecular multipole moments, in the present work extended up to hexadecapole moments, and this slightly improves the ability to reproduce the electrostatic potential. A byproduct of the ellipsoidal decomposition is a set of atomic parameters that describe the anisotropic decay of the electron density with distance from the nucleus, and this may be useful in developing anisotropic atomic parameters for use in force fields as well as for defining anisotropic atomic densities for use in quantum crystallography.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.