One-Electron Properties of Near-Hartree–Fock Wavefunctions. I. Water

Abstract

Self‐consistent‐field calculations are reported for the ground state of the water molecule in a contracted and uncontracted Gaussian basis set. The uncontracted set is shown to be near the Hartree–Fock limit for water. One‐electron properties were computed from both wavefunctions. Our best estimates for several of these quantities are: dipole moment, ${\mu }_z\text{\hspace{0.17em}=\hspace{0.17em}1.995 D}$ ; quadrupole moment, ${\theta }_{\mathrm{zz}}\text{\hspace{0.17em}=\hspace{0.17em}−\hspace{0.17em}0.108}$ and ${\theta }_{\mathrm{xx}}\text{\hspace{0.17em}=\hspace{0.17em}−\hspace{0.17em}2.422}$ in buckinghams; octupole moment, ${\Omega }_{\mathrm{xxz}}\text{\hspace{0.17em}=\hspace{0.17em}−\hspace{0.17em}1.337}$ and ${\Omega }_{\mathrm{zzz}}\text{\hspace{0.17em}=\hspace{0.17em}−\hspace{0.17em}0.960}$ in units of 10⁻³⁴ esu·cm³; average diamagnetic shielding at the proton, ${\sigma }_{\mathrm{Av}}^d\text{\hspace{0.17em}=\hspace{0.17em}102.9}$ ppm; quadrupole coupling constant at the deuteron, ${\mathrm{(eqQ\hspace{0.17em}/\hspace{0.17em}h)}}_{\mathrm{AA}}\text{\hspace{0.17em}=\hspace{0.17em}343.9}\mathrm{kc/sec}$ , and at the oxygen, ${\mathrm{(eqQ\hspace{0.17em}/\hspace{0.17em}h)}}_{\mathrm{aa}}\text{\hspace{0.17em}=\hspace{0.17em}−\hspace{0.17em}8.34 Mc\hspace{0.17em}/\hspace{0.17em}sec}$ . The effect of including d‐type Gaussian functions in the basis is examined.