Density functional theory calculations of dynamic first hyperpolarizabilities for organic molecules in organic solvent: Comparison to experiment

作者：Lu, Shih-I^*; Chiu, Cheng-Chang; Wang, Ying-Fung

来源：Journal of Chemical Physics, 2011, 135(13): 134104.

DOI：10.1063/1.3644336

• NONLINEAR-OPTICAL PROPERTIES
• GENERALIZED-GRADIENT-APPROXIMATION
• CHARGE-TRANSFER
• HARTREE-FOCK
• SEMIEMPIRICAL CALCULATIONS
• DIPOLE-MOMENT
• EXCHANGE
• RANGE
• POLARIZABILITIES
• THERMOCHEMISTRY

Against experimental values obtained from solution-phase dc electric field induced second-harmonic generation measurements at a fundamental wavelength of 1910 nm, the performance of 20 exchange-correlation functionals in density functional theory in evaluation of solvent modulated dynamic first hyperpolarizabilities of 82 organic molecules in chloroform, 1,4-dioxane, and/or dichloromethane was evaluated. The used exchange-correlation functionals consisted of generalized gradient approximation (GGA), meta-GGA, global hybrids, and range-separated hybrids. The PCM-X/6-311+G(2d,p)//PCM-B3LYP/6-31G(2df,p) level of theory was employed. The calculated results showed functionals with the exact asymptote of the exchange potential gave satisfying linear correlation with R-2 of 0.95 between experimental data and theoretical values. With a linear correction, these functionals also provided a better accuracy with mean absolute error of 5 x 10(-30) esu than other functionals. The solvent effect and solvation scheme on the calculated property were also studied.

• 出版日期2011-10-7
• 单位苏州大学