Ko Chaehyuk, Malick David K, Braden Dale A, Friesner Richard A, Martínez Todd J
Department of Chemistry and The Beckman Institute, University of Illinois, Urbana, IL 61801, USA.
J Chem Phys. 2008 Mar 14;128(10):104103. doi: 10.1063/1.2834222.
Time-dependent density functional theory (TDDFT) is implemented within the Tamm-Dancoff approximation (TDA) using a pseudospectral approach to evaluate two-electron repulsion integrals. The pseudospectral approximation uses a split representation with both spectral basis functions and a physical space grid to achieve a reduction in the scaling behavior of electronic structure methods. We demonstrate here that exceptionally sparse grids may be used in the excitation energy calculation, following earlier work employing the pseudospectral approximation for determining correlation energies in wavefunction-based methods with similar conclusions. The pseudospectral TDA-TDDFT method is shown to be up to ten times faster than a conventional algorithm for hybrid functionals without sacrificing chemical accuracy.
含时密度泛函理论（TDDFT）是在塔姆 - 丹科夫近似（TDA）框架内实现的，采用伪谱方法来计算双电子排斥积分。伪谱近似使用了一种结合谱基函数和物理空间网格的分裂表示法，以降低电子结构方法的标度行为。我们在此证明，在激发能计算中可以使用极为稀疏的网格，这是基于早期在基于波函数的方法中采用伪谱近似来确定相关能的工作，且得出了类似结论。结果表明，伪谱TDA - TDDFT方法比传统的杂化泛函算法快达十倍，同时又不牺牲化学精度。
