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

George Maroulis (1)

1 Chemistry

We report a systematic ab initio and density functional theory 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 Møller-Plesset perturbation theory and coupled-cluster calculations with large, flexible basis sets. Our best values at the second-order Møller-Plesset perturbation theory level for the mean dipole polarizability and second hyperpolarizability are α/ e2a02Eh-1 = 64.46 (-CH3), 65.59 (-CF3), 110.11 (-CCl3), 138.90 (-CBr3), 184.98 (-CI3) and γ/ e4a04Eh-3 = 21020 (-CH3), 13469 (-CF3), 32708 (-CCl3), 57599 (-CBr3), 105251 (-CI3). For comparison, the analogous MP2 values for diacetylene [P.Karamanis and G.Maroulis, Chem.Phys.Lett. 376, 403 (2003)] are α/ e2a02Eh-1 = 49.17 and γ/ e4a04Eh-3 = 16227. For the mean first hyperpolarizability we report β/ e3a03Eh-2 = -205.8 (-CH3), -55.7 (-CF3), 120.8 (-CCl3), 443.8 (-CBr3) and 725.4 (-CI3).

Mots clés: Physical Sciences

George Maroulis. An ab initio study of CX3-substitution (X = H, F, Cl, Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene. Journal of Physical Organic Chemistry, 2010, 24 (7), pp.588. ⟨10.1002/poc.1797⟩. ⟨hal-00613782⟩