具有改进色散校正的长程校正混合密度泛函

Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections.

作者信息

Lin You-Sheng, Li Guan-De, Mao Shan-Ping, Chai Jeng-Da

机构信息

Department of Physics, National Taiwan University, Taipei 10617, Taiwan.

Center for Theoretical Sciences and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan.

出版信息

J Chem Theory Comput. 2013 Jan 8;9(1):263-72. doi: 10.1021/ct300715s. Epub 2012 Nov 13.

DOI:10.1021/ct300715s

PMID:26589028

Abstract

By incorporating the improved empirical atom-atom dispersion corrections from DFT-D3 [Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. J. Chem. Phys.2010, 132, 154104], two long-range corrected (LC) hybrid density functionals are proposed. Our resulting LC hybrid functionals, ωM06-D3 and ωB97X-D3, are shown to be accurate for a very wide range of applications, such as thermochemistry, kinetics, noncovalent interactions, frontier orbital energies, fundamental gaps, and long-range charge-transfer excitations, when compared with common global and LC hybrid functionals. Relative to ωB97X-D [Chai, J.-D.; Head-Gordon, M. Phys. Chem. Chem. Phys.2008, 10, 6615], ωB97X-D3 (reoptimization of ωB97X-D with improved dispersion corrections) is shown to be superior for nonbonded interactions, and similar in performance for bonded interactions, while ωM06-D3 is shown to be superior for general applications.

摘要

通过纳入来自DFT-D3[格林姆，S.；安东尼，J.；埃利希，S.；克里格，H.《化学物理杂志》2010年，132卷，154104]改进的经验性原子-原子色散校正，提出了两种长程校正（LC）杂化密度泛函。我们得到的LC杂化泛函ωM06-D3和ωB97X-D3，与常见的全局和LC杂化泛函相比，在非常广泛的应用中，如热化学、动力学、非共价相互作用、前沿轨道能量、基本能隙和长程电荷转移激发等方面都表现出准确性。相对于ωB97X-D[柴，J.-D.；黑德-戈登，M.《物理化学化学物理》2008年，10卷，6615]，ωB97X-D3（用改进的色散校正对ωB97X-D进行重新优化）在非键相互作用方面表现更优，在键合相互作用方面性能相似，而ωM06-D3在一般应用中表现更优。