论文标题
使用DFT上的廉价糖化状态糖化：光诱导的电子和孔转移
Excited state diabatization on the cheap using DFT: Photoinduced electron and hole transfer
论文作者
论文摘要
激发的状态电子和孔转移基础是过程中的基本步骤，例如光伏异质结的激子解离，电极处的光诱导电荷转移以及光合反应中心中的电子传递。与电荷或激发局部物种相对应的绝热状态，例如局部激发和电荷转移状态，提供了一个身体直观的框架，以模拟和理解这些过程。然而，与低层电子结构方法结合使用，从绝热电子状态获得准确的绝热状态及其耦合通常会导致结果不准确，例如时间依赖性密度功能理论（TDDFT），而与高级别波力基于高效能的方法相结合时，则具有过高的计算成本。在这里，我们介绍了基于DFT的糖尿病化方案δ-Almo（MSDFT2），该方案使用绝对局部的分子轨道（ALMOS）直接构建了绝状态状态。 We demonstrate that our method, which combines ALMO calculations with the ΔSCF technique to construct electronically excited diabatic states and obtains their couplings with charge-transfer states using our MSDFT2 scheme, gives accurate results for excited state electron and hole transfer in both charged and uncharged systems that underlie DNA repair, charge separation in donor-acceptor dyads, chromophore-to-solvent electron transfer, and singlet fission.该框架是为激发状态糖尿病的准确有效构建的框架，并直接从DFT评估其耦合，从而提供了一条途径，以模拟和阐明大无序系统中的光诱导的电子和孔传递，例如在冷凝阶段遇到的途径。
Excited state electron and hole transfer underpin fundamental steps in processes such as exciton dissociation at photovoltaic heterojunctions, photoinduced charge transfer at electrodes, and electron transfer in photosynthetic reaction centers. Diabatic states corresponding to charge or excitation localized species, such as locally excited and charge transfer states, provide a physically intuitive framework to simulate and understand these processes. However, obtaining accurate diabatic states and their couplings from adiabatic electronic states generally leads to inaccurate results when combined with low-tier electronic structure methods, such as time dependent density functional theory (TDDFT), and exorbitant computational cost when combined with high-level wavefunction-based methods. Here we introduce a DFT-based diabatization scheme, Δ-ALMO(MSDFT2), which directly constructs the diabatic states using absolutely localized molecular orbitals (ALMOs). We demonstrate that our method, which combines ALMO calculations with the ΔSCF technique to construct electronically excited diabatic states and obtains their couplings with charge-transfer states using our MSDFT2 scheme, gives accurate results for excited state electron and hole transfer in both charged and uncharged systems that underlie DNA repair, charge separation in donor-acceptor dyads, chromophore-to-solvent electron transfer, and singlet fission. This framework for the accurate and efficient construction of excited state diabats and evaluation of their couplings directly from DFT thus offers a route to simulate and elucidate photoinduced electron and hole transfer in large disordered systems, such as those encountered in the condensed phase.
