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homo of -45.7, -31.1, -27.2, and -24.6 kcal/mol along M = Li, Na, K, and Rb.
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homo of -45.7, -31.1, -27.2, and -24.6 kcal/mol along M = Li, Na, K, and Rb.
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33846203560
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The description of the MO in terms of fragment MO coefficients instead of Gross Mulliken contributions yields the same picture, but it has the disadvantage of not being normalized, that is, the figures do not add up to 1 (or to 100%). Note that diffuse fragment MOs (often at higher energy) can make unphysical negative Gross Mulliken contributions, which are then compensated by positive Gross Mulliken contributions that exceed 100%. This problem occurs in a slight form also in our systems in which the sum of the main positive Gross Mulliken contributions to the C-M electron-pair bonding combination are in some cases 101%-103% (M = Li and Na in Figures 3 and 4).
-
The description of the MO in terms of fragment MO coefficients instead of Gross Mulliken contributions yields the same picture, but it has the disadvantage of not being normalized, that is, the figures do not add up to 1 (or to 100%). Note that diffuse fragment MOs (often at higher energy) can make unphysical negative Gross Mulliken contributions, which are then compensated by positive Gross Mulliken contributions that exceed 100%. This problem occurs in a slight form also in our systems in which the sum of the main positive Gross Mulliken contributions to the C-M electron-pair bonding combination are in some cases 101%-103% (M = Li and Na in Figures 3 and 4).
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77
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The C-M bond distance also increases along Li-Rb because of the increasing number of metal core shells that enter into Pauli repulsion with closed shells on the methyl fragment. For a discussion on how the interplay of bonding andrepulsive orbital interactions determines bond lengths, see, for example: Bickelhaupt, F. M, DeKock, R. L, Baerends, E. J. J. Am. Chem. Soc. 2002, 124, 1500
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The C-M bond distance also increases along Li-Rb because of the increasing number of metal core shells that enter into Pauli repulsion with closed shells on the methyl fragment. For a discussion on how the interplay of bonding andrepulsive orbital interactions determines bond lengths, see, for example: Bickelhaupt, F. M.; DeKock, R. L.; Baerends, E. J. J. Am. Chem. Soc. 2002, 124, 1500.
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