We present a proof-of-concept study of the suitability of Kruse and Grimme’s geometric counterpoise correction (gCP) for basis set superposition errors (BSSEs) in double-hybrid density functional calculations with a double-ζ basis set. The gCP approach only requires geometrical information as an input and no orbital/density information is needed. Therefore, this correction is practically free of any additional cost. gCP is trained against the Boys and Bernardi counterpoise correction across a set of 528 noncovalently bound dimers. We investigate the suitability of the approach for the B2PLYP/def2-SVP level of theory, and reveal error compensation effects—missing London dispersion and the BSSE—associated with B2PLYP/def2-SVP calculations, and present B2PLYP-gCP-D3(BJ)/def2-SVP with the reparametrised DFT-D3(BJ) and gCP corrections as a more balanced alternative. Benchmarking results on the S66x8 benchmark set for noncovalent interactions and the GMTKN55 database for main-group thermochemistry, kinetics, and noncovalent interactions show a statistical improvement of the B2PLYP-gCP-D3(BJ) scheme over plain B2PLYP and B2PLYP-D3(BJ). B2PLYP-D3(BJ) shows significant overestimation of interaction energies, barrier heights with larger deviations from the reference values, and wrong relative stabilities in conformers, all of which can be associated with BSSE. We find that the gCP-corrected method represents a significant improvement over B2PLYP-D3(BJ), particularly for intramolecular noncovalent interactions. These findings encourage future developments of efficient double-hybrid DFT strategies that can be applied when double-hybrid calculations with large basis sets are not feasible due to system size.

我们对 Kruse 和 Grimme 的几何平衡校正 (gCP) 在双 ζ 基组的双混合密度泛函计算中对基组叠加误差 (BSSE) 的适用性进行了概念验证研究。gCP 方法只需要几何信息作为输入，不需要轨道/密度信息。因此，这种修正实际上无需任何额外费用。gCP 是针对 Boys 和 Bernardi 平衡校正针对一组 528 个非共价结合的二聚体进行训练的。我们研究了该方法对 B2PLYP/def2-SVP 理论水平的适用性，并揭示了与 B2PLYP/def2-SVP 计算相关的误差补偿效应——缺少伦敦色散和 BSSE，并将 B2PLYP-gCP-D3(BJ)/def2-SVP 与重新参数化的 DFT-D3(BJ) 和 gCP 校正一起作为更平衡的替代方案。针对非共价相互作用的 S66x8 基准集和用于主族热化学、动力学和非共价相互作用的 GMTKN55 数据库的基准测试结果表明，B2PLYP-gCP-D3(BJ) 方案比普通 B2PLYP 和 B2PLYP-D3(BJ) 方案有统计改进. B2PLYP-D3(BJ) 显示出显着高估了相互作用能、势垒高度与参考值的较大偏差以及构象异构体的错误相对稳定性，所有这些都可能与 BSSE 相关。我们发现 gCP 校正方法比 B2PLYP-D3(BJ) 有显着改进，特别是对于分子内非共价相互作用。