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Ab initio determination of the electric multipole moments and static (hyper)polarizability of HCCX, X = F, Cl, Br, and I
Author(s) -
Maroulis George
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10239
Subject(s) - polarizability , multipole expansion , quadrupole , chemistry , dipole , hyperpolarizability , coupled cluster , diatomic molecule , atomic physics , ab initio quantum chemistry methods , ab initio , electronic correlation , computational chemistry , molecular physics , physics , quantum mechanics , molecule , organic chemistry
We report electric multipole moments and (hyper)polarizabilities for the haloethynes HCCX, X = F, Cl, Br, and I. The molecular properties have been obtained from finite‐field self‐consistent field, Møller–Plesset perturbation theory and coupled cluster calculations with large, carefully optimized basis sets of gaussian‐type functions. The mean dipole (hyper)polarizability and the mean quadrupole polarizability near the Hartree–Fock limit are α / e 2 a 0 2E h −1= 23.74 (HCCF), 37.26 (HCCCl), 43.97 (HCCBr), 56.44 (HCCI), β / e 3 a 0 3E h −2= −73.9 (HCCF), −67.0 (HCCCl), −39.5 (HCCBr), 42.7 (HCCI), γ / e 4 a 0 4E h −3= 4914 (HCCF), 6554 (HCCCl), 9328 (HCCBr), 14949 (HCCI), and C / e 2 a 0 4E h −1= 160.3 (HCCF), 317.1 (HCCCl), 471.2 (HCCBr), 671.2 (HCCI). Electron correlation has a small effect on the dipole polarizability but affects strongly the hyperpolarizability. Agreement with the available experimental data is more or less fair for HCCF, HCCCl, and HCCBr but less satisfactory for HCCI. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 443–452, 2003