A Robust and Accurate Tight-Binding Quantum Chemical Method for Structures, Vibrational Frequencies, and Noncovalent Interactions of Large Molecular Systems Parametrized for All spd-Block Elements ( Z = 1–86)

作者：Stefan Grimme, Christoph Bannwarth, Philip Shushkov · 发表于：Journal of Chemical Theory and Computation · 年份：2017 · DOI：10.1021/acs.jctc.7b00118 · 被引用次数：2044 · 研究领域：Advanced Chemical Physics Studies、Molecular Spectroscopy and Structure、Crystallography and molecular interactions

We propose a novel, special purpose semiempirical tight binding (TB) method for the calculation of structures, vibrational frequencies, and noncovalent interactions of large molecular systems with 1000 or more atoms. The functional form of the method is related to the self-consistent density functional TB scheme and mostly avoids element-pair-specific parameters. The parametrization covers all spd-block elements and the lanthanides up to Z = 86 using reference data at the hybrid density functional theory level. Key features of the Hamiltonian are the use of partially polarized Gaussian-type orbitals, a double-ζ orbital basis for hydrogen, atomic-shell charges, diagonal third-order charge fluctuations, coordination number-dependent energy levels, a noncovalent halogen-bond potential, and the well-established D3 dispersion correction. The accuracy of the method, called Geometry, Frequency, Noncovalent, eXtended TB (GFN-xTB), is extensively benchmarked for various systems in comparison with existing semiempirical approaches, and the method is applied to a few representative structural problems in chemistry.