Electron pair density in the lowest (1)Sigma(+)(u) and (1)Sigma(+)(g) states of H(2)
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SCOPUS
- Title
- Electron pair density in the lowest (1)Sigma(+)(u) and (1)Sigma(+)(g) states of H(2)
- Authors
- Wang, J; Kim, KS; Baerends, EJ
- Date Issued
- 2011-08-21
- Publisher
- AMER INST PHYSICS
- Abstract
- We demonstrate and advocate the use of observable quantities derived from the two-electron reduced density matrix - pair densities, conditional densities, and exchange-correlation holes - as signatures of the type of electron correlation in a chemical bond. The prototype cases of the lowest (1)Sigma(+)(u) and (1)Sigma(+)(g) states of H-2, which exhibit large variation in types of bonding, ranging from strongly ionic to covalent, are discussed. Both the excited (1)Sigma(+)(g) and (1)Sigma(+)(u) states have been interpreted as essentially consisting of (natural) orbital configurations with an inner electron in a contracted 1s sigma(g) orbital and an outer electron in a diffuse (united atom type, Rydberg) orbital. We show that nevertheless totally different correlation behavior is encountered in various states when comparing them at a common internuclear distance. Also when following one state along the internuclear distance coordinate, strong variation in correlation behavior is observed, as expected. Switches between ionic to covalent character of a state occur till very large distances (40 bohrs for states approaching the 1s3l asymptotic limit, and 282 bohrs for states approaching the 1s4l limit). (C) 2011 American Institute of Physics. [doi:10.1063/1.3624571]
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/10827
- DOI
- 10.1063/1.3624571
- ISSN
- 0021-9606
- Article Type
- Article
- Citation
- JOURNAL OF CHEMICAL PHYSICS, vol. 135, no. 7, page. 74111 - 74111, 2011-08-21
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