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16
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84989548267
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(a) Structure optimizations at the Hartree‐Fock (HF) level and with second order Møller‐Plesset perturbation theory (MP2, cf. ref. [8b]) as well as HF harmonic vibrational frequency analyses employed the Gaussian 90 and Gaussian 92 programs (cf. ref. [8c, d]). Mercury has been treated as a 20‐valence‐electron system, the 60 core electrons being replaced by an quasirelativistic multielectron‐fit pseudopotential (ref. [8 e]), as it is known that scalar relativistic effects have to be included to obtain reliable data for mercury systems (see, e.g., ref. [5]). Similar pseudopotentials have been used for Kr (8 valence electrons, ref. [8f]) and F (7 valence electrons, ref. [8g]). Contributions from spin‐orbit coupling have not been considered in the present study. The HF and MP2 calculations employed an (8s7p5d)/[6s5p3d] GTO valence basis set for Hg (ref. [8e]), a (6s6p1d)/[4s4p1d] valence basis on Kr (ref. [8f]) and (5s5p1d)/[3s3p1d] including diffuse functions on F (ref. [8h]).
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18
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84989600395
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(c) Gaussian 90, Revision F, Gaussian, Inc., Pittsburgh, PA, 1990.
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Frisch, M.J.1
Head‐Gordon, M.2
Trucks, G.W.3
Foresman, J.B.4
Schlegel, H.B.5
Raghavachari, K.6
Robb, M.7
Binkley, J.S.8
Gonzalez, C.9
DeFrees, D.J.10
Fox, D.I.11
Whiteside, R.A.12
Seeger, R.13
Melius, C.F.14
Baker, J.15
Kahn, L.R.16
Stewart, J.J.P.17
Topiol, S.18
Pople, J.A.19
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19
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84989580652
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(d) Gaussian 92, Revision A, ‐Gordon,. Gill, Gaussian, Inc., Pittsburgh PA, 1992.
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Frisch, M.J.1
Trucks, G.W.2
Head, M.3
W, P.M.4
Wong, M.W.5
Foresman, J.B.6
Johnson, B.G.7
Schlegel, H.B.8
Robb, M.A.9
Replogle, E.S.10
Gomperts, R.11
Andres, J.L.12
Raghavachari, K.13
Binkley, J.S.14
Gonzalez, C.15
Martin, R.L.16
Fox, D.I.17
DeFrees, D.J.18
Baker, J.19
Stewart, J.J.P.20
Pople, J.A.21
more..
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21
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84989564732
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Diplom Thesis, Universität Stuttgart, 1990.
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Nicklass, A.1
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22
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84989580569
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Dissertation, Universität Stuttgart, 1989.
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Dolg, M.1
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24
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0011682081
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For an explanation of the quadratic configuration interaction singles + doubles (QCISD) method and its extension by perturbation theoretical inclusion of triple excitations (QCISD, T), see for example
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(1987)
J. Chem. Phys.
, vol.87
, pp. 5968
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Pople, J.A.1
Head‐Gordon, M.2
Raghavachari, K.3
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25
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84989564695
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(a) QCISD and QCISD(T) calculations employed 8s7p5d2f, 6s6p5d3f, and 7s7p3d1f valence bases on Hg, Kr, and F, respectively, contracted in a general contraction scheme to 4s3p3d2f, 2s2p3d2f, and 3s3p2d1f. The contraction coefficients were obtained from the corresponding atomic natural orbitals (ANO, cf. ref. [10b]). All electrons outside the pseudopotential cores have been correlated. The QCI calculations used the MOLPRO92 (cf. ref. [10c]) and Gaussian (cf. ref. [8c, d]) programs.
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30
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84989536006
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2 is 1.873 Å, in good agreement with experiment (cf. ref. [7b]).
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