Development of Programs for Reaction Path Following and Spin Projection

反应路径跟踪和自旋投影程序的开发

• 批准号: 9020398
• 负责人: Hans Schlegel
• 金额: $ 24.85万
• 依托单位: Wayne State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-03-15 至 1994-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9020398&HistoricalAwards=false
• 关键词: Development; Programs; Reaction; Path; Following

In this project in the Theoretical and Computational Program of the Chemistry Division, Professor Schlegel will develop new algorithms for reaction path following on molecular potential energy surfaces. The PI uses these computational tools to study the thermodynamics and reactivity of molecules containing silicon, hydrogen and flourine that are relevant to chemical vapor deposition of amorphous silicon films for photovoltaics and etching of silicon surfaces for microelectronics. A family of five new reaction path following algorithms is proposed. Previously developed spin projection methods for correlation corrections to ground state wave functions will be extended and spin projections will be developed for CI singles calculations (single substitutions in the ground state determinantal function) of excited states. A new transition structure optimization algorithm and a new type of electric field dependent basis to calculate improved dipole moments, polarizability and infrared intensities will be developed. In the area of applications the mechanism of simple photochemical reactions will be explored. Reaction path following will be used to study the effect of solvent molecules on transition states for SN2 reactions. Transition structures and barrier heights will be determined for radical abstractions, radical additions to multiple bonds and diradical cycloaddition reactions. The study of the thermal decomposition of silicon compounds will be continued.

在化学部的理论和计算计划中，Schlegel教授将在分子势能表面上开发反应路径的新算法。 PI使用这些计算工具来研究含有硅，氢和粉的分子的热力学和反应性，这些分子与无定形硅膜的化学蒸气沉积有关，用于光伏和硅表面的硅表面以用于微电源。 提出了算法后五个新反应路径的家庭。先前开发的自旋投影方法将扩展与基础状态波函数的相关校正，并将为激发态的CI单打计算（基态决定性函数中的单个替换）开发自旋投影。将开发一种新的过渡结构优化算法和一种新型的电场依赖性基础，以计算改进的偶极矩，极化性和红外强度。在应用领域，将探索简单光化学反应的机制。反应路径以下将用于研究溶剂分子对SN2反应过渡态的影响。将确定对自由基抽象，多个键的根部添加和脏自动环加成反应的过渡结构和障碍高度。将继续对硅化合物的热分解进行研究。