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Studies of molecular Rydberg states by Schwinger variational-quantum defect methods: Application to molecular hydrogen

Stephens, J. A. and McKoy, V. (1992) Studies of molecular Rydberg states by Schwinger variational-quantum defect methods: Application to molecular hydrogen. Journal of Chemical Physics, 97 (11). pp. 8060-8072. ISSN 0021-9606. doi:10.1063/1.463428.

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An ab initio electronic structure technique has been developed to study highly excited states of molecules by combining Schwinger variational methods of collision theory with generalized quantum defect theory. The technique exploits methods of scattering theory to study the region of highly excited Rydberg levels below and across ionization thresholds for molecules. The reaction matrix K, which describes the interaction of the Rydberg electron with the ionic core, is found at arbitrary negative electron energies by employing an unbounded Coulomb Green’s function in the Lippmann–Schwinger equation for the electronic wave function. Quantal conditions are imposed to obtain discrete molecular energy levels, associated Rydbergwave functions, and quantum defect functions, all as a function of the internuclear distance. Results within the static‐exchange approximation for the ^(1,3)Σ^+_u(1σ_gnσ_u ) and ^(1,3)Π_u(1σ_gnπ_u) Rydberg states of H_2, for n=2–20 and R=1.2–5.0 a_0, are presented and discussed.

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Additional Information:© 1992 American Institute of Physics. (Received 3 August 1992; accepted 25 August 1992) Work at the California Institute of Technology was supported by grants from the National Science Foundation, Air Force Office of Scientific Research, and the Office of Health and Environmental Research of the U.S. Department of Energy. We acknowledge use of resources of the JPL/Caltech CRAY Y-MP2E/116 Supercomputer. We thank Dr. Christian Jungen for many helpful discussions, suggestions, and interest in this work, as well as for providing the unpublished quantum defect functions from Ref. 61. Travel support for this research was provided by NSF INT-9016221, and a visiting fellowship given to J.A.S. from the C.N.R.S. in the fall of 1990. Thanks are due to Dr. Mireille Aymar for providing subroutines which calculate negative energy Coulomb wave functions. J.A.S thanks Professor Chris Greene for helpful discussions and interest in this research, and Dr. Steve Pratt for pointing out Ref. 71. J.A.S. also thanks Dr. Catherine Brechignac and Dr. Michel Gaillard, and the staffs of Laboratoire Aimé Cotton and Laboratorie Photophysique Moléculaire for their hospitality during visits where portions of this research was completed.
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Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Centre National de la Recherche Scientifique (CNRS)UNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics8632
Issue or Number:11
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ID Code:61281
Deposited By: George Porter
Deposited On:20 Oct 2015 21:18
Last Modified:10 Nov 2021 22:46

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