An ab Initio and Semiempirical Study of the First- and Third-Order Polarizabilities in Benzene and Thiophene Derivatives:  Electron Correlation Effects

Abstract

The static first-and third-order polarizabilities of several benzene and thiophene derivatives are evaluated at the ab initio level via an efficacious general finite field approach. The impact of electron correlation is explored by calculating the molecular polarizabilities at the Møller-Plesset second-order perturbation (MP2) theory level using an extended basis set. Further, we examine the influence of molecular architecture on the nonlinear optical response, in particular the switch from an arylethenyl type of structure to a quinoid structure. Finally, we apply the correction vector method combined with the intermediate neglect of differential overlapsingle and double excitation configuration interaction (INDO-SDCI) technique to evaluate the optical nonlinearities at the semiempirical level. The reliability of this procedure is established by comparison with the corresponding high-level ab initio polarizability values. The results clearly show the sensitive dependence of the nonlinear optical properties on electron correlation effects that are found to quantitatively and qualitatively affect the third-order polarizability values.

Calculation of macroscopic first- and third-order optical susceptibilities for the benzene crystal

“…al [12] for the same basis set. Values for c lmno for smaller basis sets and lower level of correlation (MP2) have been given by Perrin et al [13] and Adant et al [14]. The input geometry used is the experimentally determined geometry of benzene in the gas phase [15] (CeC 0.13964 nm, CeH 0.10831 nm, symmetry h 6h ).…”

The effectiveness of essential-state models in the description of optical properties of branched push–pull chromophores

“…16,[28][29][30][31][32][33][34] Recently, semiempirical parametrizations have been used with the collective electronic oscillators (CEO) approach. [35] This method only requires the ground-state density matrix.…”

Ab initio and density functional theory calculations of the dipole polarizability and the second dipole hyperpolarizability of benzene

“…A study of linear and nonlinear optical properties of molecules such as benzene is of great interest for understanding electronic phenomena associated with the design and construction of new optical devices that might be useful in electronic communication and photonic treatments 1, 2. These properties arise from the interaction between an electromagnetic radiation field and a dielectric medium, where an oscillating polarization is induced.…”

“…It is necessary to use higher levels of theory than the HF model in order to obtain accurate values of NLO properties because electronic correlation effects are found to be important. Techniques that include electron correlations, such as Møller–Plesset perturbation theory 1, 6, coupled clusters (CC) 7, and recently, density‐functional theory (DFT) methods 8–10, have shown to give good quality NLO calculations. In particular, Møller–Plesset perturbation theory (MP2) calculations can be performed at different orders of perturbation symbolized as MP n ( n =2, 3, 4).…”