New methods for non-linear spectroscopy of molecules in complex environments by combination of coupled-cluster and polarizable embedding approaches

南加州大学的安娜·克雷洛夫得到了化学理论、模型和计算方法计划的支持，该计划旨在开发稳健而准确的理论方法和计算工具，以模拟分子与光相互作用时的性质。该奖项由高级网络基础设施部的计算和数据使能科学与工程计划共同资助。Krylov和她的研究小组对被称为非线性光学(NLO)特性的特性感兴趣。非线性光学特性被用于诸如微制造、3D光学数据存储和纳米光刻、超快电光调制和开关、生物成像、光动力学疗法以及各种其他纳米生物光子学应用等新技术中。用于解释实验光谱和用于具有与特定应用相匹配的性质的新材料的电子设计的新工具预计将影响对非线性光学性质的基础和应用研究(如生物成像和分子电子学)。这项研究产生的计算机软件通过广泛使用的Q-Chem和Spartan包提供给更广泛的研究社区。一旦成熟，该软件将以开放源代码的形式分发。这项研究的重点是复杂环境中的开壳物种和分子。拟议的发展充分利用了上一个供资期间开展的工作，其中包括发展形式和计算双光子吸收的电子因数(2PA)以及耦合集团(CC)和运动方程(EOM)系列方法中的静态和动态极化率。当前工作的主要目的是发展形式和代码：(I)通过有效片段势方法包括环境(溶剂、分子固体、蛋白质)的影响；以及(Ii)在EOM-CC框架内的高阶NLO性质，如三光子吸收矩和超极化率。新方法的计划应用包括研究非线性光谱学的基本方面，例如：(I)非线性光学性质的(非)局域性的程度以及在可极化嵌入方案中计算的这些性质相对于QM区域大小的收敛；(Ii)溶剂的静电微扰和极化响应相对于非定域激发态(例如，电荷转移到溶剂态)的贡献的相对重要性；以及(Iii)电子关联对NLO性质的影响，重点是开壳系统。将以开放源代码的形式分布，类似于我们的张量库和其他Q-CHEM模块。克里洛夫教授是南加州大学和其他地方的女性科学与工程项目的积极贡献者。她继续保持和发展理论和计算化学、材料科学和生物化学方面的女性。网页，促进妇女在这些领域的研究。

Anna Krylov of the University of Southern California is supported by an award from the Chemical Theory, Models and Computational Methods program to develop robust and accurate theoretical methods and computational tools for modeling properties of molecules when they interact with light. This award is cofunded by the Computational and Data-Enabled Science and Engineering program in the Division of Advanced Cyberinfrastructure. Krylov and her research group are interested in properties known as non-linear optical (NLO) properties. NLO properties are exploited in novel technologies such as microfabrication, 3D optical data storage and nanolithography, ultra-fast electro-optic modulation and switching, bioimaging, photodynamic therapies, and a variety of other nano-bio-photonics applications. The new tools for interpretation of experimental spectra and for the in silico design of new materials with properties matching particular application are expected to impact both fundamental and applied research (such as bioimaging and molecular electronics) on NLO properties. Computer software generated from this research are made available to the broader research community through the widely-used Q-Chem and Spartan package. Once mature, the software is distributed as open-source code. The emphasis of this research is on open-shell species and molecules in complex environments. The proposed developments capitalize on the work conducted in the previous funding period, which included developing formalisms and implementing calculations of electronic factors for two-photon absorption (2PA) and static and dynamic polarizabilities within the coupled-cluster (CC) and equation-of-motion (EOM) family of methods. The main thrust the current work is to develop the formalisms and codes: (i) to include the effect of the environment (solvent, molecular solids, proteins) via the Effective Fragment Potential method; and (ii) for higher-order NLO properties within the EOM-CC framework, such as three-photon absorption moments and hyperpolarizabilities. The planned applications of the new methods include investigations of fundamental aspects of non-linear spectroscopy, such as: (i) the extent of (non)-locality of NLO properties and the convergence of these properties computed within polarizable embedding schemes with respect to the size of the QM region; (ii) the relative importance of the electrostatic perturbation and polarization response of the solvent versus the contribution from delocalized excited states (such as charge transfer to solvent states); and (iii) the effect of electron correlation on NLO properties, with an emphasis on open-shell systems.will be distributed as open source, similarly to our tensor library and other Q-CHEM modules. Professor Krylov is an active contributor to the Women in Science and Engineering program at USC and beyond. She continues to maintain and develop the ??Women in Theoretical and Computational Chemistry, Material Science, and Biochemistry?? webpage, promoting research by women in these areas.