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

Abstract

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 R ) 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.; Tru ¨mper, 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.

Static and Dynamic Polarizabilities of Conjugated Molecules and Their Cations

“…17 Butadiene is the only polyene for which experimental polarizability has been reported, and it has also been studied with a variety of theoretical methods and a wide range of basis sets. 78,[80][81][82][83][84] The polarizabilities of butadiene calculated in the present work are 6.52, 8.10, and 8.13 Å 3 at the PBE0/6-31G(d), PBE0/6-311+G(2d,2p), and HF/ 6-311+G(2d,2p) levels of theory, respectively. The value of 8.10 Å 3 fortuitously agrees perfectly with the experimental value of 8.10 Å 3 obtained from an extrapolation of refractivity data to infinite wavelength.…”

Electric quadrupole and hexadecapole moments for X2CCX2, X = H, F, Cl, Br, and I*

“…The eventual use of these basis sets in further intermolecular interaction studies involving ethene and perhalogenated ethenes imposes strict requirements on their size and flexibility. The construction of the basis sets reflects a computational philosophy expanded in previous work 33, 42–44.…”

Donor–acceptor diethynylsilane oligomers: A second‐order nonlinear optical material

“…According to the results reported in Table 2, the introduction of the D and A groups resulted in higher values of linear polarizability (α) for the diethynylsilane derivative, but a much less extent compared with β mol , with the maximum increasing factor being only 2. The α values are several orders of magnitude higher than those for the Si 4 cluster,21 cis ‐ and trans ‐butadiene,84 and push–pull conjugated systems among others,19 which have been calculated using post‐Hartree–Fock and DFT methods. Compounds with high polarizability values are required for applications such as optical fibers.…”