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Magnetic hyperfine structure and core polarization in the excited states of lithium

Goddard, William A., III (1968) Magnetic hyperfine structure and core polarization in the excited states of lithium. Physical Review, 176 (1). pp. 106-114. ISSN 0031-899X. doi:10.1103/PhysRev.176.106.

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The magnetic hyperfine splitting constants, aJ, from theoretical calculations on the 32S, 22P, 32P, and 32D excited states of the Li atom are reported. The wave functions were calculated using the author's GF method, which corresponds to optimizing the orbitals of a Slater determinant after spin projection. Thus the wave functions include core polarization, but no appreciable correlation. For the 22P state we calculate a1 / 2=0.2206 a.u. (45.74 Mc/sec for 7Li) which is in good agreement with the experimental value, 0.2227 ± 0.0017 a.u. (46.17 ± 0.35 Mc/sec for 7Li), and the value from configuration interaction calculations, 0.2206. Thus for the Li atom core polarization accounts for most of the error in the Hartree-Fock values of aJ. These calculations yield 〈1 / r^3〉 and spin density, Q(0), in agreement with other accurate theoretical calculations, and in disagreement with the values found using level crossing experiments, indicating that the interpretation of the level crossing experiments in terms of 〈1 / r^3〉 and Q(0) may not be correct. It is found that for both the unrestricted Hartree-Fock and GF methods the use of a different Hamiltonian for each electron leads to virtual orbitals which are good approximations to the actual orbitals of excited states.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 1968 by The American Physical Society. Received 25 June 1968. Partially supported by a grant (GP-6965) from the National Science Foundation. [W.A.G., III, was an] Alfred P. Sloan Research Fellow. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 3703.
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National Science FoundationGP-6965
Alfred P. Sloan FoundationUNSPECIFIED
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Arthur Amos Noyes Laboratory of Chemical Physics3703
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ID Code:12302
Deposited By: Tony Diaz
Deposited On:24 Nov 2008 19:46
Last Modified:08 Nov 2021 22:27

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