Ding Yun, Mei Ye, Zhang John Z H, Tao Fu-Ming
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, College of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Comput Chem. 2008 Jan 30;29(2):275-9. doi: 10.1002/jcc.20788.
Systematic study has been carried out to investigate the accuracy of mid-bond functions in describing pi-pi interactions in benzene dimer. Potential energy curves are calculated for the sandwich, T-shaped, and parallel-displaced configurations of benzene dimer by adding bond functions in MP2 (second-order Møller-Plesset perturbation theory) calculations with a wide range of split-valence and augmented, correlation-consistent basis sizes. At MP2 level, the largest basis set used with a bond function (denoted aug-cc-pVDZf-6s6p4d2f) differs by only approximately 0.1 kcal/mol relative to the result obtained from the standard aug-cc-pVQZ basis calculation (without the bond function). The calculated potential energy curves from the bond function basis aug-cc-pVDZf-6s6p4d2f and the larger standard basis aug-cc-pVTZ are in excellent agreement with each other for all three configurations. The number of bond function basis aug-cc-pVDZf-6s6p4d2f is 526 compared to 828 of aug-cc-pVTZ and 1512 of aug-cc-pVQZ. Current study shows that bond functions can be effectively employed to give accurate description of pi-pi interactions with the addition of only a minimal number of bond functions.
已经开展了系统研究，以调查中键函数在描述苯二聚体中π-π相互作用时的准确性。通过在MP2（二阶莫勒-普列斯特定则微扰理论）计算中添加键函数，使用广泛的分裂价基组和增强的、相关一致的基组大小，计算了苯二聚体的夹心、T形和平行位移构型的势能曲线。在MP2水平上，使用键函数的最大基组（表示为aug-cc-pVDZf-6s6p4d2f）相对于从标准aug-cc-pVQZ基组计算（不使用键函数）得到的结果，差异仅约为0.1千卡/摩尔。对于所有三种构型，从键函数基组aug-cc-pVDZf-6s6p4d2f和更大的标准基组aug-cc-pVTZ计算得到的势能曲线彼此非常吻合。键函数基组aug-cc-pVDZf-6s6p4d2f的数量为526，而aug-cc-pVTZ为828，aug-cc-pVQZ为1512。当前研究表明，仅添加最少数量的键函数，键函数就能有效地用于准确描述π-π相互作用。
