The v-v energy transfer of highly vibrationally excitedstates (Ⅱ)──Vibrational quenching of CO(v) by H_2O

The vibrational energy transfer from highly vibrationally excited CO to H 2O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr 3 and O 2 the secondary reactions generate CO(v). The infrared emission of CO(v→v-1) is detected by TR FTIR. The excitation of H 2O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H 2O system are obtained: (1.7±0.1), (3.4±0.2), (6.2±0.4), (8.0±1.0), (9.0±2.0), (12±3), (16±4) and (18±7) (10 -13cm 3·molecule -1·s -1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH and ab initio calculations, the quenching mechanism of CO(v) by H 2O is suggested.     

The v-v energy transfer of highly vibrationally excited states (I)

The relaxation of the highly vibrationally excited CO (v = 1–8) by CO₂ is studied by timeresolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr₃ with O₂ generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v = 1–8) to CO₂ molecules areobtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10¹⁴ cm³ · molecule⁻¹ · s⁻¹), respectively. A two-channel energy transfer model can explain the feature of the quenching of CO(v) by CO². For the lower vibrational states of CO, the vibrational energy transfers preferentially to the u³ mode of CO² For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the u¹ mode of CO².     

The v-v energy transfer of highly vibrationally excited states (I)──Vibrational quenching of CO(v) by CO_2

The relaxation of the highly vibrationally excited CO (v=1-8) by CO-2 is studied by time_resolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr-3 with O-2 generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v=1-8) to CO 2 molecules are obtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10 -14 cm 3·molecule -1·s -1), respectively. A two_channel energy transfer model can explain the feature of the quenching of CO(v) by CO 2. For the lower vibrational states of CO, the vibrational energy transfers preferentially to the υ-3 mode of CO 2. For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the υ-1 mode of CO 2.     

高振动激发态的C_6H_6与N_2、O_2碰撞传能的QCT计算

准经典轨线法 (QCT)是目前理论上研究高振动激发态大分子碰撞传能的常用方法之一 ,本文用QCT方法计算了高振动激发态的C6H6 与N2 、O2 的碰撞传能 通过计算发现 ,与N2 、O2碰撞时 ,C6H6 的每次碰撞平均振动失能值与实验结果符合较好 计算结果表明 ,高振动激发态的C6H6 失去的振动能传到了N2 、O2 的振动自由度上 ,即V V传能 通过分析每一条轨线 ,发现了直接碰撞、络合碰撞及颤动碰撞三种碰撞类型 ,这与文献计算是完全一致的     

超增感过程中的能量传递

利用单光子计数技术,在纳秒级时间分辨荧光光谱仪上,通过真空升华超增感染料对薄膜的荧光寿命测试,并比较在溴化银单晶上形成的超增感体系的荧光寿命,研究了超增感过程中的能量传递,提出超增感剂的激子能带模型,并以此探讨了超增感机理。同时,对增感染料的固态薄膜的荧光光谱进行了讨论。     

水分子振动高激发态的李代数研究

用李代数方法对水分子的振动高激发态能级作了研究,与实验值相比,平均偏差为３．７４ｃｍ＾－１。     

Lie代数方法对SO2分子振动激发态的研究

利用Lie代数方法研究了SO2分子的振动激发态能谱,拟合30条光谱能级得到的RMS误差是1．66cm^-1,结果表明,所得到的分子Hamiltonian的代数展开式可以很好地再现实验能级,它预测了SO2分子振动总量子数达10的全部振动能级。     

BeO分子激发态的多参考组态相互作用计算

运用含Davidson修正的多参考组态相互作用（MRCI＋Q）方法,在Ahlrichs型TZVP基组水平上对BeO分子对应最低3个离解限Be（1SG）＋0（3PG）,Be（1SG）＋0（1DG）,Be（3PU）＋O（3PG）的共14个单重态和12个三重态在0．1nm-0．5nm范围内进行了势能扫描计算．通过对称性分析,对这26个态进行了明确标识,其中有6个单重态和6个三重态为束缚态,它们分别是X1∑＋,A1∏,21∑＋,11’△,11∑-,21∏和a3∏,b3∑＋,23∑＋,13△,23∑-,23∑-．离解能最大的3个态分别为基态x1∑＋,第一单重激发态A1∏和三重态b3∑＋,离解能分别为5．878eV,4．876eV和4．311eV．21∏态的束缚能最小,仅为0．320eV．对所有的束缚态分别进行了振动能级和转动常数的计算,进而拟合出各自的光谱学常数．     

用代数方法研究I2分子部分电子态的高阶振动能谱和离解能

鉴于I2分子电子态的振动能谱和分子离解能De在实际研究和应用中的重要性，本文应用SUN，REN等人提出的基于微扰理论的代数方法（AM），研究了I2分子A’（2u^3Ⅱ），A^3Ⅱ（1u），1g（^1D），0^＋g（^1D）和F’（0^＋u）电子态的振动光谱常数和完全振动能谱{Ev}；使用基于AM的代数能量方法（AEM）获得了这些电子态的高激发振动态的完全振动能谱和分子离解能，为许多需要这些难以从实验中获得双原子分子的精确振动光谱和离解能的科学研究提供了必要的物理数据。     

Ar原子(J=0)的高激发态结构

本文依据多通道量子亏损理论对Ar原子J=0的高激发态结构进行了理论分析,确定了基本结构参量,得到Lu-Fano图和全部分立态能位、通道混合系数,预言了自电离共振结构。     

LiB激发态的ab initio CI研究

采用ａｂｉｎｉｔｉｏＣＩ方法对ＬｉＢ的激发态进行了计算，其热能曲线表明ａΠ，Π和＾１Σ＾＋态均对应于原子基态解离遂道，（２）＾１Σ＾＝对应于原子激发态解离隧道，这些态都是束缚态，＾３Π是基态。     

掺杂非醚聚苯基喹嗯啉(PPQ)薄膜的光致发光和电致发光

用具有强蓝光发射的1,3,5-三芳基-2-吡唑啉化合物TPL对非醚聚苯基喹嗯啉（PPQ）进行掺杂,测量掺杂PPQ薄膜的光致发光和电致发光谱,根据掺杂前后PPQ薄膜的荧光谱变化,表明掺杂PPQ薄膜发光存在着基质分子和掺杂分子间的能量传递或电荷转移,掺杂PPQ薄膜的电致发光谱随外加电压变化,说明外加电压对PPQ具有调制作用。     

氦原子激发态能量的程序化计算

利用Mathematica语言开发了一个用变分法计算氦原子激发态非相对论能量的程序,对氦原子1snl(n=2→6)组态的非相对论能量进行了变分计算,理论计算值与实验值相当接近.     

高激发态的氢原子和谐振子

本文介绍了处于高激发态(n>>1)的氢原子和谐振子,其能级公式具有一致性。指出了在高激发态时氢原子与谐振子之间的联系。     

苝的振动分辨荧光光谱的理论模拟

采用密度泛函理论(DFT)模拟了苝的振动分辨的荧光光谱。在Franck-Condon近似的框架下,模拟考虑了位移谐振子近似、畸变近似和Duschinsky效应。理论模拟得到的光谱峰值与实验测得的荧光发射峰相吻合。通过对苝分子振动结构的分析发现,基态第9个振动模式对发射光谱的最大值有较大贡献,并且该振动跃迁与基态和激发态之间的结构变化相一致。