Experimental and theoretical determination of the dipole-quadrupole and dipole-octopole polarizabilities of the group IV tetrachlorides Ti Cl 4, Zr Cl4, and Hf Cl4

Abstract

The dipole-quadrupole and dipole-octopole polarizabilities A and E of Ti Cl4, Zr Cl4, and Hf Cl4 have been determined from collision-induced light-scattering experiments. Our respective experimental results for ∫A∫ are (165±10), (110±30), and (140±20) e2 a03 Eh -1, whereas ∫E∫ is determined to be (675±125), (750±200), and (670±400) e2 a04 Eh -1. Theory predicts values convincingly close to experiment, as A= (181.4±9.1), (167.6±8.4), and (139.8±7.0) e2 a03 Eh -1, and E= (-671±67), (-688±69), and (-574±57) e2 a04 Eh -1. In addition our quantum chemical ab initio calculations give reliable values for the dipole polarizability α, as well as for the octopole and hexadecapole moments Ω and Φ for all three substances. © 2006 American Institute of Physics.