Stoychev Georgi L, Auer Alexander A, Neese Frank
Max Planck Institute for Chemical Energy Conversion , Mülheim an der Ruhr 45470, Germany.
J Chem Theory Comput. 2017 Feb 14;13(2):554-562. doi: 10.1021/acs.jctc.6b01041. Epub 2017 Jan 10.
A procedure was developed to automatically generate auxiliary basis sets (ABSs) for use with the resolution of the identity (RI) approximation, starting from a given orbital basis set (OBS). The goal is to provide an accurate and universal solution for cases where no optimized ABSs are available. In this context, "universal" is understood as the ability of the ABS to be used for Coulomb, exchange, and correlation energy fitting. The generation scheme (denoted AutoAux) works by spanning the product space of the OBS using an even-tempered expansion for each atom in the system. The performance of AutoAux in conjunction with different OBSs [def2-SVP, def2-TZVP, def2-QZVPP, and cc-pwCVnZ (n = D, T, Q, 5)] has been evaluated for elements from H to Rn and compared to existing predefined ABSs. Due to the requirements of simplicity and universality, the generated ABSs are larger than the optimized ones but lead to similar errors in MP2 total energies (on the order of 10 to 10 E/atom).
开发了一种程序，可从给定的轨道基组（OBS）开始，自动生成用于恒等分辨率（RI）近似的辅助基组（ABS）。目标是为没有可用优化ABS的情况提供准确且通用的解决方案。在此背景下，“通用”被理解为ABS用于库仑、交换和相关能量拟合的能力。生成方案（称为AutoAux）通过对系统中的每个原子使用等比展开来跨越OBS的乘积空间。已针对从H到Rn的元素评估了AutoAux与不同OBS [def2-SVP、def2-TZVP、def2-QZVPP和cc-pwCVnZ（n = D、T、Q、5）]结合使用时的性能，并与现有的预定义ABS进行了比较。由于简单性和通用性的要求，生成的ABS比优化后的ABS更大，但在MP2总能量中导致的误差相似（约为10到10 E/原子）。
