Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AH, United Kingdom.
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms Universität Bonn, Beringstraße 4, 53115 Bonn, Germany.
J Chem Phys. 2018 Feb 14;148(6):064104. doi: 10.1063/1.5012601.
A revised version of the well-established B97-D density functional approximation with general applicability for chemical properties of large systems is proposed. Like B97-D, it is based on Becke's power-series ansatz from 1997 and is explicitly parametrized by including the standard D3 semi-classical dispersion correction. The orbitals are expanded in a modified valence triple-zeta Gaussian basis set, which is available for all elements up to Rn. Remaining basis set errors are mostly absorbed in the modified B97 parametrization, while an established atom-pairwise short-range potential is applied to correct for the systematically too long bonds of main group elements which are typical for most semi-local density functionals. The new composite scheme (termed B97-3c) completes the hierarchy of "low-cost" electronic structure methods, which are all mainly free of basis set superposition error and account for most interactions in a physically sound and asymptotically correct manner. B97-3c yields excellent molecular and condensed phase geometries, similar to most hybrid functionals evaluated in a larger basis set expansion. Results on the comprehensive GMTKN55 energy database demonstrate its good performance for main group thermochemistry, kinetics, and non-covalent interactions, when compared to functionals of the same class. This also transfers to metal-organic reactions, which is a major area of applicability for semi-local functionals. B97-3c can be routinely applied to hundreds of atoms on a single processor and we suggest it as a robust computational tool, in particular, for more strongly correlated systems where our previously published "3c" schemes might be problematic.
提出了一种经过修正的、适用于大型体系化学性质的 B97-D 密度泛函近似方法。与 B97-D 类似，它基于 Becke 1997 年的幂级数假设，并通过包含标准 D3 半经典色散校正进行了明确的参数化。轨道在改进的价三重-zeta 高斯基函数上展开，该基函数可用于所有元素到 Rn。其余基组误差主要被修正的 B97 参数化吸收，同时应用了一个已建立的原子对短程势来修正主族元素的键过长问题，这是大多数半局域密度泛函的典型问题。新的组合方案（称为 B97-3c）完成了“低成本”电子结构方法的层次结构，这些方法都主要没有基组叠加误差，并以物理上合理和渐近正确的方式考虑了大多数相互作用。B97-3c 给出了出色的分子和凝聚相几何形状，与在更大基组扩展中评估的大多数混合泛函相似。在全面的 GMTKN55 能量数据库上的结果表明，与同类型的泛函相比，它在主族热化学、动力学和非共价相互作用方面表现良好。这也适用于金属有机反应，这是半局域泛函的主要应用领域。B97-3c 可以在单个处理器上常规应用于数百个原子，我们建议将其作为一种稳健的计算工具，特别是对于更强烈相关的体系，我们之前发布的“3c”方案可能会存在问题。
