HNCO+OH->H2O+NCO的反应机理

采用从头算分子轨道法 (UHF/6 31G 水平 ,并用MP4加以相关能校正 )研究了HNCO OHH2 O NCO反应机理 .同时用Morokuma数值法获得了反应途径即内禀反应坐标 (IRC) .沿着IRC ,运用反应途径哈密顿理论 ,获得反应途径动态学信息 .在此基础上 ,根据过渡态理论和相应隧道效应校正 ,计算了在不同温度下的反应速率常数 ,得到了和实验相一致的结果 .计算结果表明 ,此反应是一步直接型的抽提H反应 .     

Effect of dimensionality of a crystal lattice on the properties of a localized impurity

The changes of electron density due to the presence of a localized impurity in a crystal lattice are examined in dependence on the lattice dimensionality. The Koster–Slater impurity model developed for the case of a three-dimensional simple cubic lattice has been taken as the basis of examinations. Ordinary bound states, virtual bound states, and delocalized electron states are considered in each lattice case. For the delocalized states extended in a one-dimensional lattice the amplitude of the oscillatory changes of the electron density due to the impurity perturbation does not decrease with the distance from the impurity position, whereas for a two-dimensional lattice this amplitude decreases roughly proportionally to the reciprocal value of the square root of the distance from the impurity. Let us note that a well-known amplitude characterizing the decrease of the oscillatory change of the electron density in a three-dimensional system is proportional to the reciprocal value of the third power of the distance from the impurity position. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 57–74, 2000     

Role of localized excitons in the stimulated emission in ultra-thin CdSe/ZnSe/ZnSSe single quantum-well structures

Photo-pumped lasing properties have been investigated in a CdSe/ZnSe/ZnSSE single quantum wells (SQWs) with the well-layer thickness (L_W) of 1, 2 and 3 monolayer (ML). At 20 K, the laser threshold for the SQW withL_W = 1 ML was the lowest in spite of the smallest active layer thickness. The carrier (exciton) sheet density at the threshold (n)_thwas estimated to be as low as 7 × 10¹⁰cm⁻², which is well below Mott's screening density. Time-resolved photoluminescence has revealed that the localized biexciton band, whose peak energy agrees with the lasing peak, appeared on the low-energy side of the main PL peak at this level of carrier concentrations. Theoretical calculation has also shown that the localized biexciton recombination has to be taken into account for the lasing process. On the contrary, then_thvalues of the SQWs with 2 and 3 ML are 1 order of magnitude larger than that of the SQW with 1 ML. This may be due to the smaller oscillator strength of both localized excitons and localized biexcitons because of the larger inhomogeneous broadening, resulting in an increased carrier density for achieving optical gain sufficient to overcome the reflection losses.