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：Grimme, Stefan^*; Bannwarth, Christoph; Shushkov, Philip

来源：Journal of Chemical Theory and Computation, 2017, 13(5): 1989-2009.

DOI：10.1021/acs.jctc.7b00118

• DENSITY-FUNCTIONAL THEORY
• ZETA-VALENCE QUALITY
• GAUSSIAN-BASIS SETS
• SEMIEMPIRICAL QM METHODS
• SCC-DFTB METHOD
• INTERACTION ENERGIES
• BIOMOLECULAR SIMULATION
• NDDO APPROXIMATIONS
• BENCHMARK DATABASE
• BONDING CORRECTION

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-zeta 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 comparison with existing semiempirical approaches, and the method is applied to a few representative structural problems chemistry.

• 出版日期2017-5