Range Kevin, López Carlos Silva, Moser Adam, York Darrin M
Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, USA.
J Phys Chem A. 2006 Jan 19;110(2):791-7. doi: 10.1021/jp054360q.
Five multilevel model chemistries (CBS-QB3, G3B3, G3MP2B3, MCG3/3, and MC-QCISD/3) and seven hybrid density functional methods (PBE0, B1B95, B3LYP, MPW1KCIS, PBE1KCIS, and MPW1B95) have been applied to the calculation of gas-phase basicity and proton affinity values for a series of 17 molecules relevant to the study of biological phosphoryl transfer. In addition, W1 calculations were performed on a subset of molecules. The accuracy of the methods was assessed and the nature of systematic errors was explored, leading to the introduction of a set of effective bond enthalpy and entropy correction terms. The multicoefficient correlation methods (MCG3/3 and MC-QCISD), with inclusion of specific zero-point scale factors, slightly outperform the other multilevel methods tested (CBS-QB3, G3B3, and G3MP2B3), with significantly less computational cost, and in the case of MC-QCISD, slightly less severe scaling. Four density functional methods, PBE1KCIS, MPW1B95, PBE0, and B1B95 perform nearly as well as the multilevel methods. These results provide an important set of benchmarks relevant to biological phosphoryl transfer reactions.
五种多水平模型化学方法（CBS-QB3、G3B3、G3MP2B3、MCG3/3和MC-QCISD/3）以及七种杂化密度泛函方法（PBE0、B1B95、B3LYP、MPW1KCIS、PBE1KCIS和MPW1B95）已被用于计算与生物磷酸转移研究相关的一系列17种分子的气相碱度和质子亲和能值。此外，还对一部分分子进行了W1计算。评估了这些方法的准确性，并探究了系统误差的性质，从而引入了一组有效的键焓和熵校正项。包含特定零点比例因子的多系数相关方法（MCG3/3和MC-QCISD）略优于所测试的其他多水平方法（CBS-QB3、G3B3和G3MP2B3），计算成本显著更低，就MC-QCISD而言，缩放比例也略小。四种密度泛函方法PBE1KCIS、MPW1B95、PBE0和B1B95的表现与多水平方法相近。这些结果提供了与生物磷酸转移反应相关的一组重要基准。
