Organic Dynamics in Crystalline Solids: Chemistry Near Zero Kelvin

晶体固体中的有机动力学：接近零开尔文的化学

• 批准号: 0073431
• 负责人: Miguel Garcia-Garibay
• 金额: $ 48.2万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-03-01 至 2003-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0073431&HistoricalAwards=false
• 关键词: Organic; Dynamics; Crystalline; Solids; Chemistry

With this renewal award the Organic and Macromolecular Chemistry Program continues support for the work of Dr. Miguel A. Garcia-Garibay in the Department of Chemistry and Biochemistry at the University of California, Los Angeles. The research aims at understanding chemical dynamics in highly constrained environments - crystalline organic solids at temperatures approaching absolute zero. Reactions are initiated by laser flash photolysis and studied by a variety of methods including x-ray diffraction, differential scanning calorimetry, solid state 13C NMR, and infrared and Raman spectroscopy. Quantum mechanical tunneling will be studied by means of deuterium isotope effects, anomalous Arrhenius plots of rate constants, and by theoretical and computational chemistry.The proposed work involves the changes in reactivity of highly reactive organic intermediates, generated photochemically, when these intermediates are formed not in liquid solution where there is considerable freedom of motion, but in highly constrained crystalline solids at low temperatures. Unusual products can form under these circumstances at rates that are much higher than would be expected based on rates near room temperature. Studies of this type can give insight into the detailed dynamics of the reactions involved. The work provides excellent training for students in organic synthesis, spectroscopy, kinetics, and computational chemistry. The PI actively recruits underrepresented minority students, especially Hispanics, to do research in his laboratory.

有了这个更新奖的有机和高分子化学计划继续支持博士的工作。位于洛杉矶的加州大学化学和生物化学系的Garcia-Garibay说。 该研究旨在了解高度受限环境中的化学动力学-温度接近绝对零度的结晶有机固体。 通过激光闪光光解引发反应，并通过多种方法进行研究，包括X射线衍射，差示扫描量热法，固态13 C NMR，红外和拉曼光谱。 量子力学隧穿将通过氘同位素效应、反常的Arrhenius速率常数图以及理论和计算化学来研究。拟议的工作涉及光化学产生的高活性有机中间体的反应性的变化，当这些中间体不是在有相当大的运动自由度的液体溶液中形成的，而是在低温下高度受限的结晶固体中形成的。 在这些情况下，不寻常的产物可以以比基于接近室温的速率所预期的高得多的速率形成。 这种类型的研究可以深入了解所涉及的反应的详细动力学。 这项工作为有机合成、光谱学、动力学和计算化学的学生提供了很好的训练。 PI积极招募代表性不足的少数民族学生，特别是西班牙裔学生，在他的实验室做研究。