Electrostatic calculation of linear and non-linear optical properties of ice Ih, II, IX and VIII

Macroscopic first- and third-order susceptibilities of ice Ih, ice II, ice IX and ice VIII are calculated using static and Frequency-dependent electro nic and static vibrational molecular (hyper)polarizabilities at the MP2 lev el. The molecular properties are in good agreement with experiment and with high-level ab initio calculations. Intermolecular electrostatic and polari zation effects due to induced dipoles are taken into account using a rigoro us local-field theory. The electric field due to permanent dipoles is used to calculate effective in-crystal (hyper)polarizabilities. The polarizabili ty depends only weakly on the permanent field, but the dipole moment and th e hyperpolarizabilities are strongly affected. The calculated linear suscep tibility is in good agreement with available experimental data for ice Ih, and the third-order susceptibility for a third harmonic generation experime nt is in reasonable agreement with experimental values for liquid water. Th e molecular vibrational contributions have a small effect on the susceptibi lities. The electric properties of a water tetramer are calculated and used to estimate the effect of non-dipolar interactions on the susceptibilities of ice Ih, which are found to be small. (C) 2001 Elsevier Science B.V. All rights reserved.