Spectroscopic Studies of Energy Transfer in Low Temperature Matrices

在这个项目中的物理化学计划的化学 司，吉尔伯特将研究光谱和光化学的 各种含氮和磷的小无机基团， 分子，如高能卤胺和膦， 低温基质 能量转移将在物种中进行研究 例如NX 2和PX 2，其中X = F，Cl。 生产过程中产生的中间体 还将研究M（N3）3的光解，其中M是第3族原子。 紫外/可见吸收光谱和激光诱导荧光光谱 将从基质分离种属中获得，以表征其 电子状态以及帮助理解 气相化合物的光解动力学及其 中间体的 高斯94计算将在 自由基形成。 被称为卤胺的含氮化合物家族， 以及叠氮化合物是有趣的，因为它们是 众所周知，在标准温度条件下不稳定， 压力 这种行为的原因尚不清楚，但可以肯定， 观察到的趋势是，从 含氟化合物与含氯、溴和 最后是碘。 对卤代胺中这些问题的认识 与磷化合物的比较可能有助于阐明 其他含氮和含磷物种的化学性质。 实际应用包括表面的化学蚀刻， 半导体加工、摩擦学薄膜涂层等 用于电子跃迁化学激光系统的试剂。

In this project in the Physical Chemistry Program of the Chemistry Division, Gilbert will investigate the spectroscopy and photochemistry of various nitrogen- and phosphorus-containing small inorganic radicals and molecules, such as energetic halogen amines and phosphenes, in low-temperature matrices. Energy transfer will be studied in species such as NX2 and PX2, where X = F, Cl. The intermediates produced in the photolysis of M(N3)3, where M is a Group 3 atom, will also be examined. Ultraviolet/visible absorption and laser-induced fluorescence spectra will be obtained from the matrix-isolated species to characterize their electronic states as well as to aid in understanding the photodissociation dynamics of the gas-phase compounds and their intermediates. Gaussian 94 calculations will be carried out on the radicals formed. The family of nitrogen-containing compounds known as halogen amines as well as that of azide compounds are interesting because they are notoriously unstable under standard conditions of temperature and pressure. The reasons for this behavior are not understood, but certain trends are observed, such as increasing instability in going from compounds containing fluorine to those containing chlorine, bromine, and finally iodine. An understanding of these issues in the halogen amines and comparison with the phosphorus compounds may aid in elucidating the chemical nature of other nitrogen- and phosphorus-bearing species. Practical applications include the chemical etching of surfaces in semiconductor processing, tribological thin-film coatings, and better reagents for electronic-transition chemical laser systems.