Exploring Unorthodox Dimensions for Two-Electron Atoms

被引:10
作者
Herschbach, Dudley R. [1 ,2 ]
Loeser, John G. [3 ]
Virgo, Wilton L. [1 ]
机构
[1] Texas A&M Univ, Inst Quantum Sci & Engn, College Stn, TX 77843 USA
[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
[3] Oregon State Univ, Dept Chem, Gilbert Hall 153, Corvallis, OR 97331 USA
关键词
LARGE N-EXPANSION; ELECTRON CORRELATION; CORRELATION ENERGIES; PERTURBATION-THEORY; QUANTUM-CHEMISTRY; GROUND-STATE; HELIUM; DEPENDENCE; DENSITY; MODEL;
D O I
10.1021/acs.jpca.7b06148
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Melding quantum and classical mechanics is an abiding quest of physical chemists who strive for heuristic insights and useful, tools. We present a surprisingly simple and accurate treatment of ground-state two-electron atoms. It makes use of only the dimensional dependence of a hydrogen atom, together with the exactly known first-order perturbation value of the electron electron interaction, both quintessentially quantum, and the D -> infinity limit, entirely classical. The result is an analytic formula for D-dimensional two-electron atoms with Z >= 2. For D = 3 helium, it gives accuracy better than 2 millihartrees, which is better than current density functional theory. A kindred explicit formula for correlation energy exploits interpolation between D -> infinity and D = 1 or 2; when added to the Hartree-Fock energy, it improves accuracy for D = 3 helium to better than 0.1 millihartrees.
引用
收藏
页码:6336 / 6340
页数:5
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