激发态的电荷转移激发的Hartree-Fock后继最小化方案
Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme
摘要：
光诱导电荷转移过程在新型光伏现象和光伏器件中起着关键作用。因此，从头算方法的发展，允许一个准确的和计算成本低廉的治疗电荷转移激发是一个话题，现在吸引了很多科学的关注。在本文中，我们扩展了最近介绍的单激励和双激励（M。塔西岛Theophilou和S. Thanos，国际量子化学杂志，(113)，690（2013），M.塔西岛Theophilou和S.（138），124107（2013）），以允许描述分子间电荷转移激发。我们描述了一种激发，其中电子从施主系统转移到受主系统，保持激发态与基态正交，避免变分崩溃。这些条件是通过将Hartree-Fock（HF）基态轨道所跨越的空间分解为四个子空间来实现的：位于供体分子区域的占据轨道所跨越的子空间、对应于受体分子的占据轨道所跨越的子空间以及分别位于供体和受体附近的虚轨道所跨越的两个子空间。接下来，我们创建一个斯莱特行列式，其中空穴在施主的占据轨道的子空间中，粒子在受主的虚子空间中。随后，我们通过最小化相应子空间中的HF能量泛函来优化空穴和粒子。最后，我们测试我们的方法，通过计算最低的电荷转移激发能为一组四氰基乙烯-烃类配合物，已被用作测试集，这种激发。
英文摘要：
Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations (M. Tassi, I. Theophilou and S. Thanos, Int. J. Quantum Chem., (113), 690 (2013), M. Tassi, I. Theophilou and S. Thanos, J. Chem. Phys. (138), 124107 (2013)) to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes, that have been used earlier as a test set for such kind of excitations.
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