Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Trieste, Italy.
J Comput Chem. 2022 Oct 30;43(28):1923-1935. doi: 10.1002/jcc.26992. Epub 2022 Sep 7.
A new set of auxiliary basis function suitable to fit the induced electron density is presented. Such set has been optimized in order to furnish accurate absorption spectra using the complex polarizability algorithm of time-dependent density functional theory (TDDFT). An automatic procedure has been set up, able, thanks to the definition of suitable descriptors, to evaluate the resemblance of the auxiliary basis-dependent calculated spectra with respect to a reference. In this way, it has been possible to reduce the size of the basis set maximizing the basis set accuracy. Thanks to the choice to employ a collection of molecules for each element, such basis has proven transferable to molecules outside the collection. The final sets are therefore much more accurate and smaller than the previously optimized ones and have been already included in the database of the last release of the AMS suite of programs. The availability of the present new set will allow to improve drastically the applicability range of the polTDDFT method with higher accuracy and less computational effort.
提出了一组新的辅助基函数，适用于拟合诱导电子密度。为了使用含时密度泛函理论（TDDFT）的复极化率算法准确提供吸收光谱，对该组函数进行了优化。已经建立了一个自动程序，该程序能够通过定义合适的描述符，评估辅助基相关计算光谱与参考光谱之间的相似性。通过这种方式，可以在最大程度提高基组精度的情况下，减少基组的大小。由于选择为每个元素使用一组分子，因此这种基可以转移到集合之外的分子。最终的基组因此比以前优化的基组更准确且更小，并且已经包含在 AMS 程序套件的最新版本的数据库中。新基组的出现将允许极大地提高 polTDDFT 方法的适用性范围，同时具有更高的准确性和更少的计算工作量。
