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双杂化密度泛函(及其他选定方法)的频率和零点振动能量比例因子:能否避免非谐力场?

Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods): can anharmonic force fields be avoided?

作者信息

Kesharwani Manoj K, Brauer Brina, Martin Jan M L

机构信息

Department of Organic Chemistry, Weizmann Institute of Science , 76100 Reḥovot, Israel.

出版信息

J Phys Chem A. 2015 Mar 5;119(9):1701-14. doi: 10.1021/jp508422u. Epub 2014 Oct 21.

DOI:10.1021/jp508422u
PMID:25296165
Abstract

We have obtained uniform frequency scaling factors λ(harm) (for harmonic frequencies), λ(fund) (for fundamentals), and λ(ZPVE) (for zero-point vibrational energies (ZPVEs)) for the Weigend-Ahlrichs and other selected basis sets for MP2, SCS-MP2, and a variety of DFT functionals including double hybrids. For selected levels of theory, we have also obtained scaling factors for true anharmonic fundamentals and ZPVEs obtained from quartic force fields. For harmonic frequencies, the double hybrids B2PLYP, B2GP-PLYP, and DSD-PBEP86 clearly yield the best performance at RMSD = 10-12 cm(-1) for def2-TZVP and larger basis sets, compared to 5 cm(-1) at the CCSD(T) basis set limit. For ZPVEs, again, the double hybrids are the best performers, reaching root-mean-square deviations (RMSDs) as low as 0.05 kcal/mol, but even mainstream functionals like B3LYP can get down to 0.10 kcal/mol. Explicitly anharmonic ZPVEs only are marginally more accurate. For fundamentals, however, simple uniform scaling is clearly inadequate.

摘要

我们已经获得了魏根德 - 阿尔里希斯基及其他选定基组用于MP2、SCS - MP2以及包括双杂化泛函在内的多种DFT泛函的统一频率缩放因子λ(harm)(用于谐波频率)、λ(fund)(用于基频)和λ(ZPVE)(用于零点振动能(ZPVEs))。对于选定的理论水平,我们还获得了从四次力场得到的真实非谐基频和ZPVEs的缩放因子。对于谐波频率,与CCSD(T)基组极限下的5 cm(-1)相比,双杂化泛函B2PLYP、B2GP - PLYP和DSD - PBEP86在def2 - TZVP及更大基组下,在RMSD = 10 - 12 cm(-1)时明显表现最佳。对于ZPVEs,双杂化泛函同样是表现最佳的,均方根偏差(RMSDs)低至0.05 kcal/mol,但即使是像B3LYP这样的主流泛函也能达到0.10 kcal/mol。仅显式非谐ZPVEs的精度略高。然而,对于基频,简单的统一缩放显然是不够的。

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