Ab Initio and DFT Study of the Geometric Structures and Static Dipole (Hyper)polarizabilities of Aromatic Anions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 109; no. 45; pp. 10380 - 10387
• Main Authors: Castellano, O., Bermúdez, Y., Giffard, M., Mabon, G., Cubillán, N., Sylla, M., Nguyen-Phu, X., Hinchliffe, A., Soscún, H.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17-11-2005
• Subjects: Anions - chemistry; Benzene Derivatives - chemistry; Models, Chemical; Molecular Structure; Quantum Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp051136s

The geometries and the static dipole (hyper)polarizabilities (α, β, γ) of a series of aromatic anions were investigated at the ab initio (HF, MP2, and MP4) and density functional theory DFT (B3LYP) levels of theory. The anions chosen for the present study are the benzenethiolate (Ph−S-), benzenecarboxylate (Ph−CO2 -), benzenesulfinate (Ph−SO2 -), benzenesulfonate (Ph−SO3 -), and 1,3-benzenedicarboxylate (1,3-Ph−(CO2)2 2-). For benzenethiolate anion, additional α, β, and γ calculations were performed at the coupled cluster CCSD level with MP2 optimized geometries. The standard diffuse and polarized 6-31+G(d,p) basis set was employed in conjunction to the ab initio and DFT methods. Additional HF calculations were performed with the 6-311++G(3d,3p) basis set for all the anions. The correlated electric properties were evaluated numerically within the formalism of finite field. The optimized geometries were analyzed in terms of the few reports about the phenolate and sulfonate ions. The results show that electron correlation effects on the polarizabilities are very important in all the anion series. Was found that Ph−SO2 - is highly polarizable in terms of α and β, and the Ph−S- is the highest second hyperpolarizable in the series. The results of α were rationalized in terms of the analysis of the polarization of charge based in Mulliken atomic population and the structural features of the optimized geometries of anions, whereas the large differences in the β and γ values in the series were respectively interpreted in terms of the bond length alternation BLA and the separation of charge in the aromatic ring by effects of the substitution. These results allowed us to suggest the benzenesulfinate and benzenethiolate anions as promising candidates that should be incorporated in ionic materials for second and third-order nonlinear optical devices.