Journal of Physical Chemistry A, Vol.103, No.22, 4359-4367, 1999
Determination of the complete polarizability tensor of 1,3-butadiene by combination of refractive index and light scattering measurements and accurate quantum chemical ab initio calculations
We have combined accurate quantum chemical calculations and light scattering measurements to obtain a reliable estimate of the electric dipole polarizability anisotropy of 1,3-butadiene. The theoretical investigation was based on finite-field many-body perturbation theory and coupled cluster techniques. An extensive study of basis set, electron correlation, and molecular geometry effects leads to a static value of alpha = 54.04 e(2)a(0)(2)E(h)(-1) for the mean dipole polarizability of trans-butadiene, in very good agreement with the experimental result of 54.64 e(2)a(0)(2)E(h)(-1) obtained from an extrapolation to infinite wavelength of refractivity data [Hohm, U.; Trumper, U. Ber. Bunsenges. Phys. Chem. 1992, 96, 1061]. The measured value of the dipole polarizability anisotropy of trans-butadiene is 42.5(1.7) e(2)a(0)(2)E(h)(-1) at 514.5 nm. To our knowledge, these are the first light-scattering experiments to be reported for 1,3-butadiene. The present investigation brings forth new possibilities for the extension of accurate determination of electric polarizabilities to molecules of some size, cis-Butadiene is less polarizable and less anisotropic than the trans isomer.
Keywords:BODY PERTURBATION-THEORY;ELECTRIC-DIPOLE HYPERPOLARIZABILITY;COUPLED-CLUSTER;MANY-BODY;BASIS-SET;DEPOLARIZATION RATIO;FREQUENCY-DEPENDENCE;VIRIAL-COEFFICIENTS;ORGANIC-MOLECULES;MULTIPOLE MOMENTS