Experimental and theoretical determination of the dipole-quadrupole and dipole-octopole polarizabilities of the group IV tetrachlorides TiCl4, ZrCl4, and HfCl4 -: art. no. 124312

The dipole-quadrupole and dipole-octopole polarizabilities A and E of TiCl4, ZrCl4, and HfCl4 have been determined from collision-induced light-scattering experiments. Our respective experimental results for vertical bar A vertical bar are (165 +/- 10), (110 +/- 30), and (140 +/- 20) e(2)a(0)(3)E(h)(-1), whereas vertical bar E vertical bar is determined to be (675 +/- 125), (750 +/- 200), and (670 +/- 400) e(2)a(0)(4)E(h)(-1). Theory predicts values convincingly close to experiment, as A=(181.4 +/- 9.1), (167.6 +/- 8.4), and (139.8 +/- 7.0) e(2)a(0)(3)E(h)(-1), and E=(-671 +/- 67), (-688 +/- 69), and (-574 +/- 57) e(2)a(0)(4)E(h)(-1). In addition our quantum chemical ab initio calculations give reliable values for the dipole polarizability alpha, as well as for the octopole and hexadecapole moments Omega and Phi for all three substances. (c) 2006 American Institute of Physics.