FOX-12制备过程的反应机理及动力学

采用量子化学计算方法, 在B3LYP/6-311G(d,p)水平上研究了N-脒基脲二硝基酰胺盐(FOX-12)制备过程的反应机理. 优化得到了反应势能面上各稳定点的几何构型, 通过内禀反应坐标(IRC)确认了反应物、 中间体、 过渡态及产物之间的相关性. 为了得到更可靠的反应能量和势能面信息, 进一步在MP2/6-311++G(3df,3pd)水平上对得到的构型进行能量校正, 结果表明, 先取代磺酸基通道(A1)和先取代氢通道(B)都能生成二硝基酰胺酸(HDN), 其中通道A为主反应通道; HDN可以通过HDN→FOX-12与HDN→ADN→FOX-12 两种途径转化为目标产物FOX-12, 而第2种途径为较优途径. 应用经典过渡态理论(TST)与变分过渡态理论(CVT)以及小曲率隧道效应模型校正的变分过渡态理论(CVT/SCT)计算了在200~400 K范围内各反应通道相关基元反应的速率常数, 提供了在上述温度区间内的三参数Arrhenius关系式.     

Micromechanical tunable vertical-cavity surface-emitting lasers

We report the study on a short wavelength-tunable vertical-cavity surface-emitting laser utilizing a monolithically integrated bridge tuning microelectromechanical system. A deformable-bridge top mirror suspended above an active region is utilized. Applied bridge-substrate bias produces an electrostatic force which reduces the spacing of air-gap and tunes the resonant wavelength toward a shorter wavelength (blue-shift). Good laser characteristics are obtained: such as continuous tuning ranges over 11 nm near 940 nm for 0--9 V tuning bias, the peak output power near 1 mW and the full-width-half-maximum limited to approximately 3.2--6.8 nm. A detailed simulation of the micromechanical and optical characteristics of these devices is performed, and the ratio of bridge displacement to wavelength shift has been found to be 3:1.