The Cotton–Mouton effect of liquid water. Part II: The semi-continuum model

We present gauge-origin independent calculations of the Cotton‐Mouton effect of liquid water. The liquid is represented by a semi-continuum model such that the central molecule is surrounded by its first solvation shell, which explicitly accounts for the strong interaction between the water molecule of interest and its closest neighbors. The long-range interactions with the solvent are modeled by a dielectric continuum surrounding the water molecule and the first solvation shell. We employ large basis sets, using London atomic orbitals in order to obtain gauge-origin independent results close to the Hartree‐Fock limit. It is demonstrated that the direct interaction between neighboring molecules leads to a large effect on the calculated Cotton‐Mouton constant, which undergoes a sign change from the gas to liquid phase, as observed previously for the linear electro-optical effect @K. V. Mikkelsen et al., J. Chem. Phys 102, 9362 ~1995!#. Our best estimate for the molar Cotton‐Mouton constant, 238.1i10 220 G 22 cm 3 mol 21 ~corrected for local field effects!, is in reasonable agreement with the experimental value of 2118(15)i10 220 G 22 cm 3 mol 21 . We expect that the remaining discrepancy is mainly due to an inadequate treatment of electron correlation. © 1998 American Institute of Physics.@S0021-9606~98!50102-X#

[1]  Antonio Rizzo,et al.  The Cotton-Mouton effect of liquid water. Part I: The dielectric continuum model , 1997 .

[2]  H. Ågren,et al.  The hypermagnetizability of molecular oxygen , 1997 .

[3]  K. Ruud,et al.  COTTON-MOUTON EFFECT AND SHIELDING POLARIZABILITIES OF ETHYLENE: AN MCSCF STUDY , 1997 .

[4]  K. Mikkelsen,et al.  A multipole reaction-field model for gauge-origin independent magnetic properties of solvated molecules , 1997 .

[5]  K. Ruud,et al.  The magnetizability, rotational g tensor, and quadrupole moment of PF3 revisited , 1997 .

[6]  Antonio Rizzo,et al.  The Cotton-Mouton effect in gases: Experiment and theory , 1997 .

[7]  K. Ruud,et al.  MCSCF calculations of hypermagnetizabilities and nuclear shielding polarizabilities of CO and CH4 , 1996 .

[8]  Kurt V. Mikkelsen,et al.  Molecular Response Method for Solvated Molecules in Nonequilibrium Solvation , 1996 .

[9]  Trygve Helgaker,et al.  Magnetizability and nuclear shielding constants of solvated water , 1996 .

[10]  Trygve Helgaker,et al.  Efficient parallel implementation of response theory: Calculations of the second hyperpolarizability of polyacenes , 1996 .

[11]  H. Ågren,et al.  Magnetic hyperpolarizabilities in a cubic response formulation , 1996 .

[12]  D R Yarkony,et al.  Modern electronic structure theory , 1995 .

[13]  Yi Luo,et al.  Sign change of hyperpolarizabilities of solvated water , 1995 .

[14]  Antonio Rizzo,et al.  Electric field dependence of magnetic properties: Multiconfigurational self‐consistent field calculations of hypermagnetizabilities and nuclear shielding polarizabilities of N2, C2H2, HCN, and H2O , 1995 .

[15]  P. Jørgensen,et al.  MAGNETIZABILITY OF HYDROCARBONS , 1994 .

[16]  H. Ågren,et al.  Solvent induced polarizabilities and hyperpolarizabilities of para‐nitroaniline studied by reaction field linear response theory , 1994 .

[17]  Kurt V. Mikkelsen,et al.  A multiconfiguration self‐consistent reaction field response method , 1994 .

[18]  David E. Woon,et al.  Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties , 1994 .

[19]  Trygve Helgaker,et al.  Hartree-Fock limit magnetizabilities from London orbitals , 1993 .

[20]  K. Ruud,et al.  Gauge-origin independent multiconfigurational self-consistent-field theory for vibrational circular dichroism , 1993 .

[21]  J. Torbet,et al.  Measurements of the Cotton-Mouton effect of water and of several aqueous solutions , 1992 .

[22]  David Feller,et al.  Application of systematic sequences of wave functions to the water dimer , 1992 .

[23]  T. Helgaker,et al.  An electronic Hamiltonian for origin independent calculations of magnetic properties , 1991 .

[24]  Peter Pulay,et al.  Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations , 1990 .

[25]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[26]  Trygve Helgaker,et al.  A multiconfigurational self‐consistent reaction‐field method , 1988 .

[27]  K. Mikkelsen,et al.  Electron-transfer reactions in solution. An ab initio approach , 1987 .

[28]  H. A. Levy,et al.  Liquid Water: Molecular Correlation Functions from X‐Ray Diffraction , 1971 .

[29]  J. Pople,et al.  A Theory of Magnetic Double Refraction , 1956 .

[30]  F. London,et al.  Théorie quantique des courants interatomiques dans les combinaisons aromatiques , 1937 .