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Nature of the excited states of He_2

Guberman, Steven L. and Goddard, William A., III (1975) Nature of the excited states of He_2. Physical Review A, 12 (4). pp. 1203-1221. ISSN 2469-9926. http://resolver.caltech.edu/CaltechAUTHORS:20180801-082451277

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Abstract

The low-lying excited states of He_2 have been examined using spatially projected generalized-valence-bond wave functions. Typically the excited-state potential curves are repulsive at large R (internuclear distance) but exhibit an attractive well at small R. We find that the repulsion at large R results from an unfavorable exchange interaction of a Rydberg orbital mostly on one He with the two core orbitals on the other He. This arises from the restrictions on the molecular wave function implicit in the Pauli principle and is similar in nature to the repulsive pair-pair interactions between ground state He atoms. For R < 3a_0 the Rydberg orbital is large compared with R and the shape of the potential curve is determined by core-core interactions. For the A^1Σ_u^+ state, the calculated maximum in the potential curve is 0.0607 eV at 3.09 Å, in excellent agreement with experimentally derived values. Results are presented for several other excited states.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1103/PhysRevA.12.1203DOIArticle
https://journals.aps.org/pra/abstract/10.1103/PhysRevA.12.1203PublisherArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1975 American Physical Society. Received 5 August 1974. Partially supported by Grants Nos. GP-15423 and GP-40783X from the National Science Foundation. Based on the Ph.D. thesis (California Institute of Technology, 1972) of S. L. Guberman. The authors wish to thank Dr. D. L. Huestis, Dr. Ra C. Ladner, Dr. T. H. Dunning, and Dr. R. J. Blint for many informative conversations and for the use of their computer programs and subroutines.
Funders:
Funding AgencyGrant Number
NSFGP-15423
NSFGP-40783X
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Other Numbering System NameOther Numbering System ID
WAG0075
Record Number:CaltechAUTHORS:20180801-082451277
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180801-082451277
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88423
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:01 Aug 2018 16:09
Last Modified:01 Aug 2018 16:09

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