论文标题
显式关联双重混合DFT：对GMTKN55数据库基集合的综合分析
Explicitly correlated double hybrid DFT: a comprehensive analysis of the basis set convergence on the GMTKN55 database
论文作者
论文摘要
双杂交密度功能理论（DHDFT）为接近复合波函数方法等准确性提供了诸如G4理论之类的途径。但是，glpt2（g {Ö} rling第二阶扰动理论）术语使它们部分继承了慢速$ \ propto l^{ - 3} $（带有$ l $的最大角度动量）基集基集相关波函数方法的收敛。这可以通过引入F12显式相关性来解决这：我们研究了大型和化学多样的GMTKN55（一般的主基团热化学，动力学，动力学和非共价相互作用）的DHDFT和DHDFT-F12的基础集合。 B2GP-PLYP-D3（BJ）和RevDSD-PBEP86-D4双重混合密度函数（DHDFS）被研究为测试用例，以及轨道基集合的大于AUG-CC-PV5Z和F12基集，同样大于CC-PV（Q+D）Z-F12。我们表明，F12极大地加速了DHDF的基础集合，即使是适度的CC-PVDZ-F12基集，也比CC-PV（Q+D）Z或DEF2-QZVPP在Orbital基于Orbital的方法中的质量以及CC-PV（5+D）Z的质量相比，也比CC-PV（Q+D）或def2-qzvpp更接近基集限制。令人惊讶的是，即使对于阴离子子集，也不需要Aug-CC-PVDZ-F12。总之，DHDF-F12/VDZ-F12消除了对双杂交功能的开发和应用基础收敛的担忧。质量存储和较大系统的I/O瓶颈可以通过局部对天然轨道近似可以避免，这也表现出更宽容的系统尺寸缩放。
Double-hybrid density functional theory (DHDFT) offers a pathway to accuracies approaching composite wavefunction approaches like G4 theory. However, the GLPT2 (G{ö}rling 2nd order perturbation theory) term causes them to partially inherit the slow $\propto L^{-3}$ (with $L$ the maximum angular momentum) basis set convergence of correlated wavefunction methods. This could potentially be remedied by introducing F12 explicit correlation: we investigate the basis set convergence of both DHDFT and DHDFT-F12 for the large and chemically diverse GMTKN55 (general main-group thermochemistry, kinetics, and noncovalent interactions) benchmark suite. The B2GP-PLYP-D3(BJ) and revDSD-PBEP86-D4 double hybrid density functionals (DHDFs) are investigated as test cases, together with orbital basis sets as large as aug-cc-pV5Z and F12 basis sets as large as cc-pV(Q+d)Z-F12. We show that F12 greatly accelerates basis set convergence of DHDFs, to the point that even the modest cc-pVDZ-F12 basis set is closer to the basis set limit than cc-pV(Q+d)Z or def2-QZVPP in orbital-based approaches, and in fact comparable in quality to cc-pV(5+d)Z. Somewhat surprisingly, aug-cc-pVDZ-F12 is not required even for the anionic subsets. In conclusion, DHDF-F12/VDZ-F12 eliminates concerns about basis set convergence in both the development and application of double-hybrid functionals. Mass storage and I/O bottlenecks for larger systems can be circumvented by localized pair natural orbital approximations, which also exhibit much gentler system size scaling.
