Department of Chemistry, Soochow University, No. 70, Lin-Shih Road, Taipei City 111, Taiwan.
J Chem Phys. 2011 Oct 7;135(13):134104. doi: 10.1063/1.3644336.
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 × 10(-30) esu than other functionals. The solvent effect and solvation scheme on the calculated property were also studied.
针对在 1910nm 基频下通过溶液相直流电场感应二次谐波产生测量获得的实验值，评估了密度泛函理论中 20 种交换相关泛函在评估 82 种有机分子在氯仿、1,4-二氧六环和/或二氯甲烷中溶剂调制动态第一超极化率方面的性能。所用的交换相关泛函包括广义梯度近似（GGA）、meta-GGA、全局杂化和范围分离杂化。采用了 PCM-X/6-311+G(2d,p)//PCM-B3LYP/6-31G(2df,p)理论水平。计算结果表明，具有交换势能精确渐近的泛函与实验值和理论值之间的 R(2)为 0.95 的线性相关性令人满意。通过线性校正，这些泛函的平均绝对误差为 5×10(-30)esu，也比其他泛函具有更好的精度。还研究了溶剂效应和溶剂化方案对计算性质的影响。
