Non-linear optical properties and absolute structure of metastable 4-methyl benzophenone

Abstract

Abstract Metastable 4-methyl benzophenone (4-MBP, C14H12O) crystallizes in the polar (pyroelectric) and enantiomorphic space groups (SG) P31 and P32. The optical rotation tensor has been measured for 670 nm and the material was tested for evidence of phase-matchability. The absolute structure was determined via three-beam diffraction, showing that the structural right-hand screw 31 is combined with positive (right-handed, i.e. clockwise when looking towards the light source) optical rotation, for both tensor components ρ 11 = ρ 22 = 26(5)°/mm, ρ 33 = 8.3(5)°/mm (contrary to low-quartz which shows negative optical rotation for ρ 33 and positive rotation for ρ 11 in right-hand SG P312). The non-linear optical tensors for optical rotation, d-coefficients, electro-optic effect and electrogyration have been calculated using a set of electronic polarizabilities as input parameters for a dipole-dipole interaction model that reproduces the experimental refractive indices and optical rotation. Unusually high polarizability volumes are needed for hydrogen atom bonding to aromatic carbons in order to model the optical tensors. The non-linear optical coefficients are of medium size.