Static and dynamic polarizabilities and first hyperpolarizabilities for CH4, CF4, and CCl4

Complete polarizabilities and first hyperpolarizabilities (which include zero-point-vibrational averaging and other vibrational corrections) have been calculated at the self-consistent-field and Møller–Plesset second order perturbation levels of approximation for CH4, CF4, and CCl4. As well as the static values, α(−ω;ω), β(−ω;ω,0), and β(−2ω;ω,ω) have also been determined. The values of β(−2ω;ω,ω) for CCl4 are germane to a proposed standard for the determination of nonlinear optical properties in solution. For CCl4, our best estimate of β(−2ω;ω,ω) at ℏω = 0.040 a.u. is 13.6 a.u., the experimentally-derived gas value at ℏω = 0.043 a.u. is 20.7± 1.6 a.u. This latter value has been used to substantiate the proposed liquid phase value.