Study of the structure of molecular complexes. IV. The Hartree‐Fock potential for the water dimer and its application to the liquid state

The Hartree‐Fock energy of the water dimer has been computed for 216 different nuclear configurations using the basis set given in the first paper of this series. Near the equilibrium configuration, a calculation was carried out using a large Gaussian basis set with optimized orbital exponents for the oxygen 3d ‐ and 4f ‐type and hydrogen 2p ‐ and 3d ‐type functions in order to get results close to the Hartree‐Fock limit. In the vicinity of the equilibrium configuration the mechanism for binding of the dimer is analyzed with the help of the bond energy analysis formalism. The importance of polarization (internal charge transfer), as pointed out previously by a number of authors, is clearly evident. The computed energies have been used to derive a simple analytical expression that reproduces the Hartree‐Fock potential energy surface to a high degree of accuracy. This analytical potential is compared with the empirical effective pair potentials proposed by Rowlinson and Ben‐Naim and Stillinger for the descr...

[1]  J. A. Barker,et al.  Structure of water; A Monte Carlo calculation , 1969 .

[2]  E. Clementi,et al.  Study of the structure of molecular complexes. II. Energy surfaces for a water molecule in the field of a sodium or potassium cation , 1973 .

[3]  J. S. Rowlinson,et al.  The lattice energy of ice and the second virial coefficient of water vapour , 1951 .

[4]  E. Clementi,et al.  Study of the structure of molecular complexes. III. Energy surface of a water molecule in the field of a fluorine or chlorine anion , 1973 .

[5]  A. Narten.  Liquid Water: Atom Pair Correlation Functions from Neutron and X‐Ray Diffraction , 1972 .

[6]  P. Kollman,et al.  Theory of the Hydrogen Bond: Electronic Structure and Properties of the Water Dimer , 1969 .

[7]  Frank H. Stillinger,et al.  Molecular Dynamics Study of Temperature Effects on Water Structure and Kinetics , 1972 .

[8]  J. W. Moskowitz,et al.  One-Electron Properties of Near-Hartree-Fock Wavefunctions. I. Water , 1968 .

[9]  J. D. Bernal,et al.  A Theory of Water and Ionic Solution, with Particular Reference to Hydrogen and Hydroxyl Ions , 1933 .

[10]  K. Morokuma,et al.  Molecular‐Orbital Studies of Hydrogen Bonds. An Ab Initio Calculation for Dimeric H2O , 1968 .

[11]  E. Clementi,et al.  Study of the Structure of Molecular Complexes. I. Energy Surface of a Water Molecule in the Field of a Lithium Positive Ion , 1972 .

[12]  G. Diercksen.  SCF-MO-LCGO studies on hydrogen bonding. The water dimer , 1971 .