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85034293515
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note
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Because there is only a shallow minimum, one might question the appropriateness of these FOCI wave functions with fairly small basis sets for calculating the spin-orbit coupling constants. Actually, the qualitative nature of the wave function (e.g., positive Mulliken charge on Xe) is well reproduced even at this moderate level of theory, and the relative energies of the different states should also be acceptably well described. Some test calculations were performed, with the aim of probing the sensitivity of the spin-orbit coupling constants and of the SO corrections to the ground state energy to the level of theory. Thus, the basis set was changed, the CAS space was enlarged, the level of CI treatment was changed from only single excitations to no excitations (CAS wave functions only) or to single and double excitations (SOCI wave functions). All of these tests showed only small differences from the present results, which suggests that the FOCI wave functions used here are appropriate, at least within the approximate one-electron operator formalism applied.
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D. Schrōder, N. Goldberg, W. Zummack, H. Schwarz, J. C. Poutsma, and R. R. Squires, Int. J. Mass Spectrom. Ion Processes 165/166, 71 (1997); G. Hornung, C. A Schalley, M. Dieterle, D. Schröder, and H. Schwarz, Chem. Eur. J. 3, 1866 (1997); C. A. Schalley, G. Hornung, D. Schrōder, and H. Schwarz, Int. J. Mass Spectrom. Ion Processes 172/173. 181 (1998); Chem. Soc. Rev. 27, 91 (1998).
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67
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85034282304
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note
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1 vector was always of negligible magnitude (0.02 or smaller).
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70
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0348114671
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For neutral NeH* as a similar example, see S. F. Selgren, D. E. Hipp, and G. I. Gellene, J. Chem. Phys. 88, 3116 (1988).
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Gellene, G.I.3
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