Quantum Chemical Methods for Studying Photon and Electron Driven Processes

研究光子和电子驱动过程的量子化学方法

• 批准号: 2303111
• 负责人: Spiridoula Matsika
• 金额: $ 48.46万
• 依托单位: Temple University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-04-01 至 2026-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2303111&HistoricalAwards=false
• 关键词: Quantum; Chemical; Methods; Studying; Photon

With support from from the Chemical Theory, Models and Computational Methods program in the Division of Chemistry, Professor Spiridoula Matsika of Temple University is developing and applying computational tools to study chemical reactions and other phenomena initiated by light or electrons. Heat, photons (light), and electrons provide different energy sources to initiate chemical reactions. While reactions initiated by heat and light are well studied, electron-induced reactions are less well understood, even though they play a crucial role in biology, chemistry, and technology. Professor Matsika and her research group are developing efficient and accurate methods to describe processes initiated by electrons. The developed methods will be tested by comparisons with experimental spectra provided by collaborators, and they will be applied to study reactions related to biological damage, astrochemistry and catalysis. Of special importance will be reactions involved in radiation damage to components of DNA, related to cancer and cancer therapies. This work will have broader impacts in the education of graduate and undergraduate students as well as postdoctoral fellows. Dr. Matsika will also make efforts to enhance involvement of students from underrepresented groups in research and science. This research plan will give the opportunity to postdoctoral fellows, as well as graduate and undergraduate students to get training in theoretical methods development and in applications of quantum mechanical methods to challenging problems.A major problem with electron-driven processes is that the states formed when an electron is attached to a molecular system are often metastable and can decay fast via autodetachment, so one must treat them properly as resonances. Since resonances are not bound states, conventional quantum chemical methods cannot be applied, and modifications are needed to describe the energies and lifetimes of these metastable states. To make progress in the theoretical description of electron-driven processes the Matsika group will focus on the following objectives: 1) Efficient multireference methods combined with complex absorbing potentials will be developed. 2) These methods will be used to explore complex potential energy surfaces and conical intersections between complex surfaces. On the fly dynamics for temporary anions will be performed, and spectroscopic observables (such as time resolved photoelectron spectra) will be calculated. 3) The methods will be benchmarked by collaboration with experimental groups. The Matsika group will focus on a range of applications that aim at a better understanding of interactions of electrons with molecules relevant to biology, astrochemistry, and catalysis. Particularly, the team seeks to obtain a more complete picture of electron-induced damage to biomolecules, particularly nucleobases. The methodology developed will be implemented in open-source software.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学理论、模型和计算方法项目的支持下，天普大学的 Spiridoula Matsika 教授正在开发和应用计算工具来研究由光或电子引发的化学反应和其他现象。 热、光子（光）和电子提供不同的能源来引发化学反应。虽然热和光引发的反应已得到充分研究，但电子引发的反应却不太了解，尽管它们在生物学、化学和技术中发挥着至关重要的作用。 Matsika 教授和她的研究小组正在开发高效、准确的方法来描述电子引发的过程。所开发的方法将通过与合作者提供的实验光谱进行比较来进行测试，并将应用于研究与生物损伤、天体化学和催化相关的反应。特别重要的是涉及与癌症和癌症治疗相关的 DNA 成分辐射损伤的反应。这项工作将对研究生、本科生以及博士后的教育产生更广泛的影响。马齐卡博士还将努力加强代表性不足群体的学生对研究和科学的参与。 该研究计划将为博士后研究员以及研究生和本科生提供接受理论方法开发和量子力学方法应用来解决挑战性问题方面的培训的机会。电子驱动过程的一个主要问题是，当附着在分子系统上的电子通常是亚稳态的，并且可以通过自动脱离而快速衰减，因此必须将它们正确地视为共振。由于共振不是束缚态，因此无法应用传统的量子化学方法，需要进行修改来描述这些亚稳态的能量和寿命。为了在电子驱动过程的理论描述方面取得进展，Matsika 小组将重点关注以下目标：1）将开发与复杂吸收势相结合的高效多参考方法。 2）这些方法将用于探索复杂的势能表面和复杂表面之间的圆锥相交。将执行临时阴离子的动态动力学，并计算光谱可观测值（例如时间分辨光电子能谱）。 3）这些方法将通过与实验组的合作进行基准测试。 Matsika 小组将专注于一系列应用，旨在更好地理解电子与生物学、天体化学和催化相关分子的相互作用。特别是，该团队寻求更全面地了解电子对生物分子（尤其是核碱基）造成的损伤。所开发的方法将在开源软件中实施。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Using transition density models to interpret experimental optical spectra of exciton-coupled cyanine (iCy3)2 dimer probes of local DNA conformations at or near functional protein binding sites

使用转变密度模型解释功能蛋白结合位点或附近局部 DNA 构象的激子耦合花青 (iCy3)2 二聚体探针的实验光谱

• DOI: 10.1093/nar/gkad1163
• 发表时间: 2023-12
• 期刊: Nucleic Acids Research
• 影响因子: 14.9
• 作者: Heussman, Dylan;Enkhbaatar, Lulu;Sorour, Mohammed I.;Kistler, Kurt A.;von Hippel, Peter H.;Matsika, Spiridoula;Marcus, Andrew H.
• 通讯作者: Marcus, Andrew H.

Excited state hydrogen or proton transfer pathways in microsolvated n -cyanoindole fluorescent probes

微溶剂化n-氰基吲哚荧光探针中的激发态氢或质子转移途径

• DOI: 10.1039/d3cp04844f
• 发表时间: 2024-01
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Salsabil Abou-Hatab;Spiridoula Matsika
• 通讯作者: Spiridoula Matsika