Thakkar Ajit J
Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada.
J Chem Phys. 2020 Sep 28;153(12):124307. doi: 10.1063/5.0025662.
Experimental, theoretical, and additive-model photoabsorption cross sections combined with constraints provided by the Kuhn-Reiche-Thomas sum rule and the high-energy behavior of the dipole oscillator strength density are used to construct dipole oscillator strength distributions for benzene, pyridazine (1,2-diazine), pyrimidine (1,3-diazine), pyrazine (1,4-diazine), s-triazine (1,3,5-triazine), toluene (methylbenzene), hexafluorobenzene, and nitrobenzene. The distributions are used to predict dipole sum rules S(k) for -6 ≤ k ≤ 2, mean excitation energies I(k) for -2 ≤ k ≤ 2, and isotropic van der Waals C coefficients. A popular combination rule for estimating C coefficients for unlike interactions from the C coefficients of the like interactions is found to be accurate to better than 1% for 606 of 628 cases (96.4%) in the test set.
结合库恩 - 赖歇 - 托马斯求和规则以及偶极振子强度密度的高能行为所提供的约束条件,利用实验、理论和加和模型光吸收截面来构建苯、哒嗪(1,2 - 二嗪)、嘧啶(1,3 - 二嗪)、吡嗪(1,4 - 二嗪)、均三嗪(1,3,5 - 三嗪)、甲苯(甲基苯)、六氟苯和硝基苯的偶极振子强度分布。这些分布用于预测 -6 ≤ k ≤ 2 时的偶极求和规则 S(k)、-2 ≤ k ≤ 2 时的平均激发能 I(k) 以及各向同性范德华 C 系数。对于测试集中628个案例中的606个(96.4%),一种用于从同类相互作用的 C 系数估算异类相互作用 C 系数的常用组合规则被发现其准确度优于1%。