MOMENTUM-SPACE AND COULOMB CORRELATION - A 2-PARTICLE DENSITY ANALYSIS FOR THE H-2(1-SIGMA-G+) MOLECULE

Citation
Ke. Banyard et J. Sanders, MOMENTUM-SPACE AND COULOMB CORRELATION - A 2-PARTICLE DENSITY ANALYSIS FOR THE H-2(1-SIGMA-G+) MOLECULE, The Journal of chemical physics, 99(7), 1993, pp. 5281-5294
Citations number
65
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
ISSN journal
00219606
Volume
99
Issue
7
Year of publication
1993
Pages
5281 - 5294
Database
ISI
SICI code
0021-9606(1993)99:7<5281:MACC-A>2.0.ZU;2-0
Abstract
Electron correlation in momentum space is assessed for the ground-stat e of H2 by examining changes in the two-particle probability density e valuated over preselected momentum planes. The associated radial and a ngular ''planar Coulomb shifts,'' DELTAR(p12) and DELTAA(epsilon(p)), are also calculated. This study complements an earlier analysis for H- 2 in position space. The natural expansion of the correlated wave func tion used previously was converted into momentum space by means of a D irac-Fourier transform. As before, correlation effects are measured wi th respect to the description provided by the first natural configurat ion. Characteristics of the three components of Coulomb correlation fo r a linear molecule are highlighted by specific choices for the moment um of a ''test'' or ''reference'' electron. Unlike position space, it was found that one component worked in distinct opposition to the othe r components, a feature analogous to atomic studies in momentum space. The trends observed throughout a series of probability changes in mom entum space for H-2 were rationalized and linked to the correlation be havior in position space.