Departamento de Química, Universidad de Guadalajara, CUCEI, Blvd. Marcelino García Barragán 1421, C. P. 44430 Guadalajara, Jalisco, Mexico.
Departamento de Electrónica, Universidad de Guadalajara, CUCEI, Blvd. Marcelino García Barragán 1421, C. P. 44430 Guadalajara, Jalisco, Mexico.
J Chem Phys. 2020 Jan 7;152(1):014105. doi: 10.1063/1.5130174.
The working equations for the calculation of the electron paramagnetic resonance (EPR) g-tensor within the framework of the auxiliary density functional theory (ADFT) are presented. The scheme known as gauge including atomic orbitals (GIAOs) is employed to treat the gauge origin problem. This ADFT-GIAO formulation possesses an inherent high computational performance, allowing for the calculation of the EPR g-tensor of molecules containing some hundreds of atoms in reasonable computational time employing moderate computational resources. The effect of the use of a gauge independent auxiliary density on the quality of the g-tensor calculation for the evaluation of the exchange-correlation contribution is analyzed in this work. The best agreement with the experiment is obtained with the BLYP functional (Becke 1988 exchange and Lee-Yang-Parr correlation) in combination with a double-ζ basis set, in particular aug-cc-pVDZ. Furthermore, models of endohedral fullerenes N@C, with n = {60, 70, 100, 180, 240}, were used for benchmarking its computational performance.
提出了在辅助密度泛函理论（ADFT）框架内计算电子顺磁共振（EPR）g 张量的工作方程。采用称为包含原子轨道的规范（GIAO）方案来处理规范原点问题。这种 ADFT-GIAO 公式具有内在的高计算性能，允许在合理的计算时间内使用中等计算资源计算包含数百个原子的分子的 EPR g 张量。本工作分析了在评估交换相关贡献时使用独立规范辅助密度对 g 张量计算质量的影响。与实验最佳吻合的是 BLYP 函数（Becke 1988 交换和 Lee-Yang-Parr 相关）与双ζ基组（特别是 aug-cc-pVDZ）的组合。此外，还使用了笼内富勒烯 N@C 的模型（n = {60,70,100,180,240}）对其计算性能进行基准测试。
