Nachwuchsgruppe Theorie-SFB 569, Universität Ulm, Albert-Einstein-Allee 11, D-89081 Ulm, Germany.
Chemphyschem. 2011 Dec 9;12(17):3383-91. doi: 10.1002/cphc.201100499. Epub 2011 Nov 8.
Four common parametrisations of spin-component-scaled second-order Møller-Plesset (MP2) theory are benchmarked by calculating the anharmonic vibrational frequencies of a test suite consisting of eighteen diatomic and five small molecules. Of the four methods, the scaled opposite-spin MP2 (SOS-MP2), the variable-scaling opposite-spin MP2 (VOS-MP2) and the spin-component-scaled MP2 (SCS-MP2) methods perform statistically better than standard MP2 theory, while the spin-component scaled for nucleic bases MP2 (SCSN-MP2) performs worse. Vibrations of closed-shell diatomic molecules are slightly more accurately described by the SOS-MP2 method of Head-Gordon (ε(MAD) =51 cm(-1) ) than the SCS-MP2 method of Grimme (ε(MAD) =61 cm(-1)) or the size-consistent parametrisation of VOS-MP2 (ε(MAD) =54 cm(-1)). For open-shell diatomic molecules, the SOS-MP2 (ε(MAD) =83 cm(-1)) and SCS-MP2 (ε(MAD) =81 cm(-1)) methods are of similar accuracy, while VOS-MP2 is slightly better (ε(MAD) =77 cm(-1)). Since the VOS-MP2 and SOS-MP2 methods tend to have smaller deviations from experiment, and they can be made computationally more economical than the SCS-MP2 or MP2 methods, we suggest that they should be the preferred ab initio method for computing vibrational frequencies in large molecules.
四种常见的自旋分量标度二阶 Møller-Plesset（MP2）理论参数化方法，通过计算由十八个双原子分子和五个小分子组成的测试套件的非谐振动频率进行基准测试。在这四种方法中，标度相反自旋 MP2（SOS-MP2）、可变标度相反自旋 MP2（VOS-MP2）和自旋分量标度 MP2（SCS-MP2）方法在统计学上优于标准 MP2 理论，而碱基的自旋分量标度 MP2（SCSN-MP2）方法表现更差。闭壳层双原子分子的振动稍微更准确地描述为 Head-Gordon 的 SOS-MP2 方法（ε（MAD）=51 cm(-1)），而不是 Grimme 的 SCS-MP2 方法（ε（MAD）=61 cm(-1)）或 VOS-MP2 的大小一致参数化方法（ε（MAD）=54 cm(-1)）。对于开壳层双原子分子，SOS-MP2（ε（MAD）=83 cm(-1)）和 SCS-MP2（ε（MAD）=81 cm(-1)）方法的精度相似，而 VOS-MP2 方法略好（ε（MAD）=77 cm(-1)）。由于 VOS-MP2 和 SOS-MP2 方法与实验的偏差较小，并且它们在计算上比 SCS-MP2 或 MP2 方法更经济，因此我们建议它们应该是计算大分子振动频率的首选从头算方法。
