利用DFT进行廉价的激发态非糖尿病化：光诱导电子和空穴转移
Excited state diabatization on the cheap using DFT: Photoinduced electron and hole transfer
摘要：
激发态电子和空穴转移是光伏异质结激子解离、电极光诱导电荷转移和光合反应中心电子转移等过程的基础。对应于电荷或激发局域物种的非绝热态，例如局部激发态和电荷转移态，提供了一个物理直观的框架来模拟和理解这些过程。然而，从绝热电子态获得精确的非绝热态和它们的耦合通常导致当与低层电子结构方法（例如时间相关密度泛函理论（TDDFT））组合时的不准确结果，以及当与基于高水平波函数的方法组合时的过高计算成本。在这里，我们介绍了一个基于DFT的非绝热化方案，Δ-ALMO（MSDFT 2），它直接使用绝对定域分子轨道（ALMO）构建非绝热态。我们证明，我们的方法，结合ALMO计算与ΔSCF技术来构建电子激发非绝热态，并获得他们的耦合与电荷转移状态，使用我们的MSDFT 2方案，给出了准确的结果激发态电子和空穴转移的带电和不带电的系统，DNA修复，电荷分离的供体-受体二联体，生色团到溶剂的电子转移，和单线态裂变的基础。这种框架的准确和有效的建设激发态diabats和直接从DFT评估他们的耦合，从而提供了一条路线来模拟和阐明光诱导的电子和空穴转移在大型无序系统，如在凝聚相遇到的。
英文摘要：
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.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
