Simulating UV/vis and circular dichroism spectra for large-scale molecular systems under pressure

在物理或光谱性质上表现出压力诱导变化的材料引起多种有用的应用。在分子尺度上完全揭示潜在现象所需的理论研究落后于该领域的实验进展。虽然以前无法实现，但最近随着GOSTSHYP的发展，前者的基础已经奠定，作为第一个明确纳入由施加压力引起的电子密度变化的压力模型。本文提出的研究工作的目的是推导和实现扩展到这种形式主义，使光谱模拟通过线性响应理论。实施工作将在VeloxChem程序代码中进行，该程序代码是为高效利用高性能计算资源而开发的。随后，一系列的计算，涉及苯分子和集群的各种大小的实施方法，以捕捉实验观察到的现象的能力，以及阐明内和分子间的相互作用对压力引起的性质变化的影响。最后，在对螺烯分子的大规模研究中，将研究作为重要性质的圆二色性及其与实验观察到的结构变化的相关性。总的来说，所提供的实施和获得的见解预计将保持潜在的引导未来发展的所需性能的压致变色材料。

Materials exhibiting pressure-induced changes in physical or spectroscopic properties give rise to a manifold of useful applications. The theoretical studies that are needed to fully unravel the underlying phenomena at the molecular scale lag behind the experimental advancements in the field. While out of reach previously, a foundation for the former was laid recently with the development of GOSTSHYP, as the first pressure model that explicitly incorporates the change in the electron density introduced by the applied pressure. The aim of the research work proposed herein is to derive and implement an extension to this formalism enabling spectroscopy simulations by means of linear response theory. The implementation work will be carried out in the VeloxChem program code, developed for efficient utilization of high-performance computing resources. Subsequently, a series of calculations involving benzene molecules and clusters of various sizes should demonstrate the ability of the implemented methodology to capture experimentally observed phenomena, as well as elucidate the interplay between intra- and intermolecular effects on pressure-induced property changes. Lastly, in a large-scale study on helicene molecules the pressure-dependency of, e.g., circular dichroism as important property and its correlation with experimentally observed structural changes will be investigated. Overall, the provided implementation and obtained insights are expected to hold the potential to steer future developments of piezochromatic materials of desired properties.