Electronic Couplings for Charge Transfer across Molecule/Metal and Molecule/Semiconductor Interfaces: Performance of the Projector Operator-Based Diabatization Approach
Electronic Couplings for Charge Transfer across Molecule/Metal and Molecule/Semiconductor Interfaces: Performance of the Projector Operator-Based Diabatization Approach
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DOI：
10.1021/acs.jpcc.7b06566
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发表时间：
2017-09-14
影响因子：
3.7
通讯作者：
Blumberger, Jochen
中科院分区：
文献类型：
--
作者：
Futera, Zdenek;Blumberger, Jochen
决定分子和金属之间电荷转移速率的一个主要参数是分子的离散电子态和金属的带态之间的电子耦合强度。他们用计算化学方法进行计算，无论是在概念上还是在实践中都是具有挑战性的。在这里，我们报告了Kondov等人（J. Phys.）的投影算子非核化（POD）方法的实施。化学。C 2007, 111, 11970-11981)在CP2K程序包，它扩展了应用范围，在无限周期表面的电荷转移。在POD方法中，整个体系的自一致Kohn-Sham哈密顿量被划分为块对角化的供体（如分子）和受体（如金属）块。用非对角线块的矩阵元素简单地确定了施主和受主状态之间的耦合矩阵元素。我们发现POD方法在HAB11数据库上的表现与约束DFT （CDFT）相似，对于简单有机二聚体之间的多余空穴转移，其平均相对无符号误差为9.3%，而CDFT的平均相对无符号误差为5.3%。通过研究两个例子，从染料分子向TiO2的电子注入和从形成自组装单层的分子向金属Au（111）的电子转移，我们证明了POD方法是一种有用且具有成本效益的工具，用于估计异质界面上的电子耦合。
One principal parameter determining charge transfer rates between molecules and metals is the electronic coupling strength between the discrete electronic states of the molecule and the band states of the metal. Their calculation with computational chemistry methods remains challenging, both conceptually and in practice. Here, we report the implementation of the projection-operator diabatization (POD) approach of Kondov et al. (J. Phys. Chem. C 2007, 111, 11970-11981) in the CP2K program package, which extends the range of applications to charge transfer at infinite periodic surfaces. In the POD approach the self-consistent Kohn-Sham Hamiltonian of the full system is partitioned in donor (e.g., molecule) and acceptor (e.g., metal) blocks which are block-diagonalized. The coupling matrix elements between donor and acceptor states are simply identified with the matrix elements of the off-diagonal block. We find that the POD method performs similarly well as constrained DFT (CDFT) on the HAB11 database for excess hole transfer between simple organic dimers, with, a mean relative unsigned error of 9.3 %, compared to 5.3 % in CDFT. By studying two case examples, electron injection from a dye molecule to TiO2 and electron transfer from a molecule, that forms self-assembled monolayers, to metallic Au(111), we demonstrate that the POD method is a useful and cost-effective tool for estimation of electronic coupling across heterogeneous interfaces.