Dispersion-Corrected Spin-Component-Scaled Double-Hybrid Density Functional Theory: Implementation and Performance for Non-covalent Interactions

作者：Roch, Loic M.; Baldridge, Kim K.^*

来源：Journal of Chemical Theory and Computation, 2017, 13(6): 2650-2666.

DOI：10.1021/acs.jctc.7b00220

• GENERALIZED GRADIENT APPROXIMATION
• POTENTIAL-ENERGY FUNCTIONS
• LIGHT-EMITTING-DIODES
• AUXILIARY BASIS-SETS
• SOLID-STATE PACKING
• HYDROGEN-STORAGE
• CORANNULENE DERIVATIVES
• BENCHMARK CALCULATIONS
• DIATOMIC-MOLECULES
• INVERSION BARRIER

The implementation of 300 combinations of generalized gradient approximation/local density approximation exchange correlation dispersion-corrected spin-component scaled double-hybrid (DSD) density functional theory (DFT) methods has been carried out and the performance assessed against several DFT and post-Hartree-Fock methods, enabling further advancements toward the long-standing challenge of accurate prediction of interaction energies and associated properties. The resulting framework is flexible and has been further extended to include the resolution of identity (RI) approximation for solving the critical four-center two-electron repulsion integrals in the basis of the Kohn Sham orbitals for cost effectiveness. To evaluate the performance of this set of new cost-effective methods, denoted as RI-DSD-DFTs, seven validation data sets were designed to cover a broad range of non-covalent interactions with characteristic stabilizing contributions. Inclusion of the perturbative treatment of correlation effects is shown to significantly improve the description of weak interactions. The set of DSD-DFTs.provide interaction energies with root-mean-square deviations and mean absolute errors within 0.5 kcal/mol. The cost-effective RI-DSD-DFT counterparts deviate by less than 0.18 kcal/mol on average with only 2% of the computational cost.

• 出版日期2017-6
• 单位天津大学