Arey J Samuel, Aeberhard Philippe C, Lin I-Chun, Rothlisberger Ursula
Laboratory of Computational Chemistry and Biochemistry, Swiss Federal Institute of Technology at Lausanne (EPFL), Switzerland.
J Phys Chem B. 2009 Apr 9;113(14):4726-32. doi: 10.1021/jp810323m.
In recent works, dispersion-corrected atom-centered potentials (DCACPs) were developed as a method to account for long-range dispersion forces between molecules in density functional theory calculations within the generalized gradient approximation (GGA). Here, we test the ability of DCACPs to improve the GGA treatment of hydrogen-bonded systems. We assessed both BLYP and dispersion-corrected BLYP with respect to benchmark calculations for the hydrogen bond lengths and binding energies of 20 complexes containing the elements C, H, N, O, and S. Benchmark data included geometries calculated using MP2 and CCSD(T) and binding energies using W2, W1, CBS-QB3, and other CCSD(T) extrapolation schemes. With respect to benchmark methods, dispersion-corrected BLYP exhibited a mean signed error of 0.010 A in the hydrogen bond length and a mean relative error of 5.1% in the hydrogen bond binding energy. By comparison, uncorrected BLYP exhibited error statistics of 0.036 A and 15.9%, respectively. We conclude that DCACPs robustly improve the BLYP description of hydrogen-bonded systems at small additional computational cost. New benchmark geometries (MP2/aug-cc-pVTZ) and new benchmark binding energies (W1) are presented for seven complexes, and the remaining benchmark data were taken from previous literature.
在最近的研究中，开发了色散校正的原子中心势（DCACPs），作为一种在广义梯度近似（GGA）下的密度泛函理论计算中考虑分子间长程色散力的方法。在此，我们测试了DCACPs改善GGA对氢键体系处理的能力。我们针对包含C、H、N、O和S元素的20个配合物的氢键长度和结合能的基准计算，评估了BLYP和色散校正的BLYP。基准数据包括使用MP2和CCSD(T)计算的几何结构，以及使用W2、W1、CBS-QB3和其他CCSD(T)外推方案计算的结合能。相对于基准方法，色散校正的BLYP在氢键长度上的平均符号误差为0.010 Å，在氢键结合能上的平均相对误差为5.1%。相比之下，未校正的BLYP的误差统计分别为0.036 Å和15.9%。我们得出结论，DCACPs以较小的额外计算成本有力地改善了BLYP对氢键体系的描述。给出了七个配合物的新基准几何结构（MP2/aug-cc-pVTZ）和新基准结合能（W1），其余基准数据取自先前的文献。
