Employing Range Separation on the meta-GGA Rung: New Functional Suitable for Both Covalent and Noncovalent Interactions

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• 作者：Marcin Modrzejewski ; Michal Hapka ; Grzegorz Chalasinski ; Malgorzata M. Szczesniak
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：August 9, 2016
• 年：2016
• 卷：12
• 期：8
• 页码：3662-3673
• 全文大小：731K
• 年卷期：0
• ISSN：1549-9626

文摘

We devise a scheme for converting an existing exchange functional into its range-separated hybrid variant. The underlying exchange hole of the Becke-Roussel type has the exact second-order expansion in the interelectron distance. The short-range part of the resulting range-separated exchange energy depends on the kinetic energy density and the Laplacian even if the base functional lacks the dependence on these variables. The most successful practical realization of the scheme, named LC-PBETPSS, combines the range-separated Perdew–Burke–Ernzerhof (PBE) exchange lifted to the hybrid meta-generalized gradient approximation rung and the Tao–Perdew–Staroverov–Scuseria (TPSS) correlation. The value of the range-separation parameter is estimated theoretically and confirmed by empirical optimization. The D3 dispersion correction is recommended for all energy computations employing the presented functional. Numerical tests show remarkably robust performance of the method for noncovalent interaction energies, barrier heights, main-group thermochemistry, and excitation energies.