Static electric dipole polarizability and hyperpolarizability of fluorodiacetylene ☆

Abstract

We report finite-field Møller–Plesset perturbation theory and coupled cluster calculations of the dipole moment and static (hyper)polarizability of fluorodiacetylene (F–CC–CC–H). A large basis set of [5s3p3d2f/5s3p3d2f/3s3p2d] type, consisting of 237 contracted gaussian-type functions, yields SCF values of μ z =0.3312 e a 0 for the dipole moment, α ̄ =49.37 and Δ α=55.29 e 2 a 0 2 E h −1 for the mean and the anisotropy of the dipole polarizability, β ̄ =−182.06 e 3 a 0 3 E h −2 and γ ̄ =9626 e 4 a 0 4 E h −3 for the mean of the first and second dipole hyperpolarizability, respectively. Electron correlation has a very small effect on the dipole polarizability but affects strongly the hyperpolarizability. The [5s3p3d2f/5s3p3d2f/3s3p2d] basis yields for the second dipole hyperpolarizability MP2 values (SCF results in parentheses), γ ̄ =12,489 (9626), Δ 1 γ=59,147 (31,532) and Δ 2 γ=7461 (1735) e 4 a 0 4 E h −3. Fluorodiacetylene is less (hyper)polarizable than diacetylene at the SCF level of theory.