ESTER AMINOLYSIS - STRUCTURE-REACTIVITY RELATIONSHIP AND RATE-DETERMINING STEP IN AMINOLYSIS OF SUBSTITUTED DIPHENYL CARBONATES
ESTER AMINOLYSIS - STRUCTURE-REACTIVITY RELATIONSHIP AND RATE-DETERMINING STEP IN AMINOLYSIS OF SUBSTITUTED DIPHENYL CARBONATES
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DOI：
10.1021/ja00463a032
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
JENCKS, WP
中科院分区：
文献类型：
--
作者：
GRESSER, MJ;JENCKS, WP
我们的结果表明，在适当的条件下，利用高能红外激光脉冲的多光子吸收，可以诱导中等尺寸的有机分子发生非平衡反应。需要在较低的压力和较高的激光强度下进行这样的实验，以最大限度地减少VV和VT。分子间驰豫可能是一个普遍的要求，特别是对于V-V驰豫速率为气体动力学碰撞频率的>；0.1的大的多原子分子。由于非平衡激光诱导的反应路径遵循能量最低的单分子路径，并且由于激光路径与碰撞弛豫在1托范围内是竞争的，因此意味着被吸收的激光能量在分子内的重新松弛。6·10感谢由美国化学学会管理的石油研究基金的捐赠者对这项研究的部分支持；美国国家科学基金会承认美国国家科学基金会(MPS75-02793-NSF)。我们感谢Robert S.F.Chang在这项工作的初始阶段提供的专家帮助，感谢Harold C.Breshears执行RRKM计算，并感谢堪萨斯州立大学研究生院在采购Capítol设备方面的帮助。
Our results demonstrate that under appropriate conditions a moderate-sized organic molecule can be induced to undergo a nonequilibrium reaction by multiple photon absorption from a high energy infrared laser pulse. The need to conduct such experiments at lower pressure and rather high laser intensities to minimize VV and VT. R intermolecularrelaxation may be a general requirement particularly forlarge polyatomic molecules for which V-V relaxation rates are> 0.1 of the gas kinetic collision frequency. Since the nonequilibrium laserinduced reaction pathway follows the unimolecular pathway of lowest energy and since the laser pathway is competitive with collisional relaxation in the 1-Torr range, intramolecular re-laxation of the absorbedlaser energy is implied. 6· 10Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research (WCD and WDM); DWS acknowledges that National Science Foundation (MPS75-02793-NSF). We are grateful for the expert assistance provided by Robert S. F. Chang in the initial stages of this work, to Harold C. Breashears for performing the RRKM calculations, and to the Graduate School, Kansas State University, for assistance in purchasing capítol equip-ment.