This work is dedicated to the theoretical investigation of the influence of water clusters' organisation and size on the electronic spectrum of an interacting benzene (Bz) molecule using both TD-DFT and CASPT2 approaches. Two series of geometries, namely $Geo_{IEI}$ and $Geo_{IED}$ were extracted from two Bz-hexagonal ice configurations leading to maximum and minimum ionization energies respectively. An appropriate basis set containing atomic diffuse and polarisation orbitals and describing the Rydberg states of Bz was determined. The TD-DFT approach was carefully benchmarked against CASPT2 results for the smallest systems.Despite some discrepancies, the trends were found to be similar at both levels of theory: the positions and intensities of the main $π\rightarrow π^{\star}$ transitions were found slightly split due to symmetry breaking. For the smallest systems, our results clearly show the dependence of the electronic transitions on the clusters' structures. Of particular interest, low energy transitions of non negligible oscillator strength from a Bz $π$ orbital to a virtual orbital of Rydberg character, also involving atomic diffuse functions and partially expanded on the water cluster, were found for the $Geo_{IED}$ series. The energies of such transitions were determined to be more than 2\,eV below the ionization potential of Bz. When the cluster's size increases, similar transitions were found for all structures, the virtual orbitals becoming mainly developed on the H atoms of the water molecules at the edge of the cluster. Given their nature and energy, such transitions could play a role in the photochemistry of aromatic species in interaction with water clusters or ice, such processes being of astrophysical interest.
Vibrational Activation Triggers Ultrafast Excited State Intramolecular Proton Transfer in Single-Benzene Fluorophores
Sorbonne Universit\'e, CNRS, Institut des NanoSciences de Paris, 4 place Jussieu, 75005 Paris, France；Sorbonne Universit\'e, CNRS, Laboratoire de Chimie Th\'eorique, 4 place Jussieu, 75005 Paris, France
The vibrational properties of benzene on an ordered water ice surface
本文提出了一种CCSD（T）+PBE-D3混合方法来计算气相苯和苯吸附在有序水-冰表面的振动特征。我们比较我们的方法对实验记录的光谱和计算使用PBE-D3的方法（谐波和非谐波）的结果。计算使用质子有序XIh水冰表面组成的288个水分子，并与实验记录的ASW冰表面的光谱结果进行比较。我们显示的重要性，包括水冰表面光谱计算，由于所得的振动模式，频率和强度的红外光谱中看到的过渡。的整体强度图案转移从一个占主导地位的$ν_{11}$带在气相中的几个高强度载体的红外光谱的吸附苯。当用于吸附苯时，本文提出的混合方法实现了21 cm $^{-1}$的IR活性模式的RMSD，而非谐波和谐波PBE-D3方法分别为72 cm $^{-1}$和49 cm $^{-1}$。与实验相比，我们的气态苯混合模型也获得了最佳结果，与非谐波和谐波PBE-D3方法的55 cm $^{-1}$和31 cm $^{-1}$相比，IR活性模式的RMSD为24 cm $^{-1}$。为了便于分配，我们生成并提供了一个对应关系图的正常模式的气体和吸附的苯分子。最后，我们计算的频率偏移，$Δν$，吸附苯相对于其气相突出的表面相互作用对振动带的影响，并评估我们选择的色散校正密度泛函理论的适用性。
Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding
密度泛函理论（DFT）对弱相互作用复合物的研究主要集中在范德华色散力的重要性上，而对交换作用的研究则少之又少。在这里，通过利用水和硼和氮掺杂的苯衍生物（1，2-氮杂硼）之间的微妙的结合，我们展示了如何精确的交换可以改变复杂的结合构象。基准值已经计算了三个方向的水单体的1，2-氮杂硼杂环从明确相关的量子化学方法，我们也使用扩散量子蒙特卡罗。对于一个流行的DFT交换相关泛函的主机，我们表明，缺乏确切的交换导致错误的最低能量方向的水对1，2-氮杂硼杂环。因此，我们建议，高比例的确切交换和相关的电子结构的改善可能需要掺杂表面上的物理吸附位点和复杂的有机分子的准确预测。同时，为了预测正确的绝对相互作用能，需要通过色散包含泛函来增强对交换的准确描述，并且某些非局部范德华泛函（optB 88-和optB 86 b-vdW）对于绝对相互作用能表现得非常好。通过与水在苯和环硼氮烷（B $_3$ N $_3$ H $_6$）上的比较，我们表明这些结果可能对水与掺杂石墨烯表面的相互作用具有影响，并提出了调节相互作用能的可能方式。
The small impact of various partial charge distributions in ground and excited state on the computational Stokes shift of 1-methyl-6-oxyquinolinium betaine in diverse water models
Computing solvated excited states using fragment-effective-field coupled-cluster perturbation theory with application to the electronic spectra of nucleobases in water
The rust challenge -- On the correlations between electronic structure, excited state dynamics and photoelectrochemical performance of hematite photoanodes for solar water splitting
The Photochemical Birth of the Hydrated Electron in Liquid Water
The Abdus Salam International Center for Theoretical Physics（阿卜杜斯·萨拉姆国际理论物理中心）；École Polytechnique Fédérale de Lausanne（洛桑联邦理工学院）；Flatiron Institute（平顿研究所）；Pacific Northwest National Laboratory（太平洋西北国家实验室）
Excited-state nonadiabatic dynamics in explicit solvent using machine learned interatomic potentials
Research Platform on Accelerating Photoreaction Discovery (ViRAPID), University of Vienna（维也纳大学加速光反应发现研究平台（ViRAPID））；Vienna Doctoral School in Chemistry, University of Vienna（维也纳大学维也纳化学博士学院）；Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna（维也纳大学化学学院理论化学研究所）；Department of Chemistry, Sapienza University of Rome（罗马大学化学系）；Wilhelm-Ostwald Institute, University of Leipzig（莱比锡大学威廉·奥斯特瓦尔德研究所）
