Thermochemistry and Geometries for Transition-Metal Chemistry from the Random Phase Approximation

• DOI: 10.1021/acs.jctc.6b00756
• Publication Date: 2016-10-17T18:23:18Z
• Authors: Craig Waitt; Nashali M. Ferrara; Henk Eshuis
• Keywords: Thermochemistry; Random phase approximation

Performance of the random phase approximation (RPA) is tested for thermochemistry and geometries transition-metal chemistry using various benchmarks obtained either computationally or experimentally. Comparison made to popular (semi)local meta- hybrid density functionals as well second-order Møller–Plesset perturbation theory (MP2) its spin-component-scaled derivatives. The benchmark sets include reaction energies, barrier heights, dissociation energies prototype bond-activation reactions, a set large complexes, bond lengths metal hydride ions, angles closed-shell first-row complexes. emphasis on chemistry, though elements beyond are included. Attention paid basis convergence RPA. For thermochemistry, RPA performs par better than functional (DFT) presented significantly more accurate MP2. largest errors observed in where electronic environment altered substantially. structural parameters, very good results were obtained, meets high quality structures from DFT. In most cases, well-converged with triple-zeta quality. MP2 optimized values can often not be average inferior Though chemical accuracy reached, method step forward toward systematic, parameter-free, all-round describe chemistry.