An ab initio study of CX3-substitution (X = H, F, Cl, Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene

作者：Karamanis Panaghiotis; Maroulis George^*

来源：Journal of Physical Organic Chemistry, 2011, 24(7): 588-599.

DOI：10.1002/poc.1797

• hyperpolarizability
• polarizability
• substituted diacetylene

We report a systematic ab initio and density functional theory (DFT) study of the electric properties of the X3C-C C-C C-H (X = H, F, Cl, Br, and I) sequence of substituted diacetylenes. We rely on finite-field Moller-Plesset perturbation theory and coupled-cluster calculations with large, flexible basis sets. Our best values at the second-order Moller-Plesset perturbation theory level for the mean dipole polarizability and second hyperpolarizability are (alpha) over bar /e(2)a(0)(2)E(h)(-(1)) = 64.46 (-CH3), 65.59 (-CF3), 110.11 (-CCl3), 138.90 (-CBr3), 184.98 (-Cl-3) and (gamma) over bar /e(4)a(0)(4)E(h)(-(3)) = 21020 (-CH3), 13469 (-CF3), 32708 (-CCl3), 57599 (-CBr3), and 105251 (-Cl-3). For comparison, the analogous MP2 values for diacetylene [P.Karamanis and G.Maroulis, Chem. Phys. Lett. 2003, 376, 403.] are (alpha) over bar /e(2)a(0)(2)E(h)(-(1)) =49.17, and (gamma) over bar /e(4)a(0)(4)E(h)(-(3)) = 16227. For the mean first hyperpolarizability we report (beta) over bar /e(3)a(0)(3)E(h)(-(2)) = 205.8 (-CH3), -55.7 (-CF3), 120.8 (-CCl3), 443.8 (-CBr3), and 725.4 (-Cl-3).

• 出版日期2011-7