Static electric dipole polarizability and hyperpolarizability of fluorodiacetylene

We report finite-field Moller-Plesset perturbation theory and coupled cluster calculations of the dipole moment and static (hyper)polarizability of fluorodiacetylene (F-Cequivalent toC-Cequivalent toC-H). A large basis set of [5s3p3d2f/5s3p3d2f/3s3p2d] type, consisting of 237 contracted gaussian-type functions, yields SCF values of mu(z) = 0.3312 e a(0) for the dipole moment, (alpha) over bar = 49.37 and Deltaalpha = 55.29 e(2) a(0)(2) E-h(-1) for the mean and the anisotropy of the dipole polarizability, (beta) over bar = - 182.06 e(3) a(0)(3) E-h(-2) and (gamma) over bar = 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), (gamma) over bar = 12,489 (9626), Delta(1 gamma) = 59,147 (31,532) and Delta(2) gamma = 7461 (1735) e(4) a(0) (4) E-h(-3). Fluorodiacetylene is less (hyper)polarizable than diacetylene at the SCF level of theory. (C) 2003 Elsevier Science B.V. All rights reserved.