Liu Lei, Brandenburg Jan Gerit, Grimme Stefan
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn, Beringstrasse 4, 53115 Bonn, Germany.
London Centre for Nanotechnology, University College London, 17-19 Gordon Street, WC1H 0AH London, UK.
Philos Trans A Math Phys Eng Sci. 2017 Aug 28;375(2101). doi: 10.1098/rsta.2017.0006.
Recently, the concept of small molecule activation by frustrated Lewis pairs (FLPs) has been expanded to the solid state showing a variety of interesting reactivities. Therefore, there is a need to establish a computational protocol to investigate such systems theoretically. In the present study, we selected several FLPs and applied multiple levels of theory, ranging from a semi-empirical tight-binding Hamiltonian to dispersion corrected hybrid density functionals. Their performance is benchmarked for the computation of crystal geometries, thermostatistical contributions, and reaction energies. We show that the computationally efficient HF-3c method gives accurate crystal structures and is numerically stable and sufficiently fast for routine applications. This method also gives reliable values for the thermostatistical contributions to Gibbs free energies. The meta-generalized gradient approximated TPSS-D3 evaluated in a projector augmented plane wave basis set is able to produce sufficiently accurate reaction electronic energies. The established protocol is intended to support experimental studies and to predict new reactions in the emerging field of solid-state FLPs.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.
最近，受阻路易斯酸碱对（FLPs）激活小分子的概念已扩展到固态，展现出各种有趣的反应活性。因此，有必要建立一种计算方法从理论上研究此类体系。在本研究中，我们选择了几种FLPs，并应用了多个理论水平，从半经验紧束缚哈密顿量到色散校正的杂化密度泛函。对它们在计算晶体几何结构、热统计贡献和反应能量方面的性能进行了基准测试。我们表明，计算效率高的HF-3c方法能给出准确的晶体结构，在数值上稳定且速度足够快，可用于常规应用。该方法还能给出热统计对吉布斯自由能贡献的可靠值。在投影增强平面波基组中评估的元广义梯度近似TPSS-D3能够产生足够准确的反应电子能量。所建立的方法旨在支持实验研究，并预测固态FLPs新兴领域中的新反应。本文是主题为“受阻路易斯酸碱对化学”特刊的一部分。
