Natural bond orbital analysis of near-Hartree–Fock water dimer

Journal of Chemical Physics - Tập 78 Số 6 - Trang 4066-4073 - 1983
Alan E. Reed1, Frank Weinhold1
1Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706

Tóm tắt

We have carried out a natural bond orbital analysis of hydrogen bonding in the water dimer for the near-Hartree–Fock wave function of Popkie, Kistenmacher, and Clementi, extending previous studies based on smaller basis sets and less realistic geometry. We find that interactions which may properly be described as ‘‘charge transfer’’ (particularly the n-σ*OH interaction along the H-bond axis) play a critical role in the formation of the hydrogen bond, and without these interactions the water dimer would be 3–5 kcal/mol repulsive at the observed equilibrium distance. We discuss this result in relationship to Klemperer’s general picture of the bonding in van der Waals molecules, and to previous theoretical analyses of hydrogen bonding by the method of Kitaura and Morokuma.

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Tài liệu tham khảo

1972, J. Chem. Phys., 56, 2242

1970, J. Chem. Phys., 53, 1686, 10.1063/1.1674245

1981, Rev. Sci. Instrum., 52, 33, 10.1063/1.1136443

1981, J. Chem. Phys., 74, 813, 10.1063/1.441183

1976, Can. J. Phys., 54, 487, 10.1139/p76-056

1981, J. Chem. Phys., 74, 6539, 10.1063/1.441113

1981, J. Chem. Phys., 75, 5285, 10.1063/1.441968

1975, J. Chem. Phys., 63, 881, 10.1063/1.431368

1980, J. Chem. Phys., 73, 3523, 10.1063/1.440734

1981, J. Chem. Phys., 74, 4936, 10.1063/1.441746

1982, J. Chem. Phys., 76, 292, 10.1063/1.442778

1982, J. Chem. Phys., 76, 4857, 10.1063/1.442804

1976, Annu. Rev. Phys. Chem., 27, 553, 10.1146/annurev.pc.27.100176.003005

1979, Chem. Phys. Lett., 66, 108, 10.1016/0009-2614(79)80378-4

1975, Theor. Chim. Acta (Berlin), 36, 249, 10.1007/BF00549690

1973, J. Chem. Phys., 59, 1325, 10.1063/1.1680187

1974, J. Chem. Phys., 60, 2929, 10.1063/1.1681463

1980, J. Am. Chem. Soc., 102, 7211, 10.1021/ja00544a007

1980, Int. J. Quantum Chem. Symp., 14, 201

1972, J. Chem. Phys., 57, 1077, 10.1063/1.1678361

1957, Phys. Rev., 105, 102, 10.1103/PhysRev.105.102

1975, J. Chem. Phys., 63, 2162, 10.1063/1.431596

1970, J. Chem. Phys., 52, 5001, 10.1063/1.1672736

1976, Int. J. Quantum Chem., 10, 325, 10.1002/qua.560100211

1977, J. Am. Chem. Soc., 99, 1316, 10.1021/ja00447a007

1979, J. Chem. Phys., 71, 517, 10.1063/1.438059

1982, J. Chem. Phys., 76, 4573, 10.1063/1.443535

1982, J. Chem. Phys., 77, 1166, 10.1063/1.443981

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Thông tin xuất bản

Journal of Chemical Physics

Tập 78 Số 6

4066-4073

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