Angelotti Wagner F D, Angelotti Lucila C Z, Haiduke Roberto L A
Instituto de Ciências Tecnológicas e Exatas, Departamento de Matemática Aplicada, Universidade Federal do Triângulo Mineiro, Uberaba, Brazil.
Centro Universitário Barão de Mauá, São Paulo, Brazil.
J Comput Chem. 2025 Jul 30;46(20):e70187. doi: 10.1002/jcc.70187.
Density functional theory (DFT) is a treatment widely employed for exploring the electronic structure of atoms, molecules, solids, and complex systems. Despite its efficiency and popularity, the accuracy of DFT results is highly dependent on the choice of exchange-correlation (XC) functionals. This study evaluates several XC functionals for calculating atomization energies in 13-atom homo- and heteronuclear alkali metal clusters (X and YX, with X, Y = Li, Na, K, Rb, and Cs), comparing these results with reference data obtained from fixed-node Diffusion Monte Carlo (DMC) simulations. Our findings emphasize the critical role of the correlation functional in achieving more accurate results. Moreover, empirical dispersion corrections are shown to be quite important for these systems. Notably, PBE and PBE0 functionals with D3-BJ dispersion seem particularly reliable for atomization energy calculations in these clusters.
密度泛函理论（DFT）是一种广泛用于探索原子、分子、固体和复杂体系电子结构的方法。尽管DFT效率高且广受欢迎，但其结果的准确性高度依赖于交换关联（XC）泛函的选择。本研究评估了几种XC泛函用于计算13原子同核和异核碱金属团簇（X和YX，其中X、Y = 锂、钠、钾、铷和铯）的原子化能，并将这些结果与从固定节点扩散蒙特卡罗（DMC）模拟获得的参考数据进行比较。我们的研究结果强调了关联泛函在获得更准确结果方面的关键作用。此外，经验色散校正对于这些体系显得非常重要。值得注意的是，带有D3-BJ色散的PBE和PBE0泛函在这些团簇的原子化能计算中似乎特别可靠。
