Department of Chemistry, Duke University, Durham, NC 27708-0346, USA.
Phys Chem Chem Phys. 2010 Jan 14;12(2):416-21. doi: 10.1039/b916688b. Epub 2009 Nov 13.
Time-dependent density functional theory (TDDFT) has broad application in the study of electronic response, excitation and transport. To extend such application to large and complex systems, we develop a reformulation of TDDFT equations in terms of non-orthogonal localized molecular orbitals (NOLMOs). NOLMO is the most localized representation of electronic degrees of freedom and has been used in ground state calculations. In atomic orbital (AO) representation, the sparsity of NOLMO is transferred to the coefficient matrix of molecular orbitals (MOs). Its novel use in TDDFT here leads to a very simple form of time propagation equations which can be solved with linear-scaling effort. We have tested the method for several long-chain saturated and conjugated molecular systems within the self-consistent charge density-functional tight-binding method (SCC-DFTB) and demonstrated its accuracy. This opens up pathways for TDDFT applications to large bio- and nano-systems.
时间依赖密度泛函理论（TDDFT）在电子响应、激发和输运的研究中有广泛的应用。为了将这种应用扩展到大型和复杂的系统，我们提出了一种基于非正交局域分子轨道（NOLMO）的 TDDFT 方程的重构。NOLMO 是电子自由度的最局域表示，已用于基态计算。在原子轨道（AO）表示中，NOLMO 的稀疏性被转移到分子轨道（MO）的系数矩阵。它在 TDDFT 中的新颖应用导致了非常简单的时间传播方程形式，可以用线性标度的努力来求解。我们已经在自洽电荷密度泛函紧束缚方法（SCC-DFTB）内对几个长链饱和和共轭分子系统进行了方法测试，并证明了其准确性。这为 TDDFT 在大型生物和纳米系统中的应用开辟了道路。
