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.     

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.     

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     

分子高激发振动态的经典非线性性质

该文阐述如何运用经典非线性力学的概念,来理解分子高激发振动态的谱学性质.内容包括:莫尔斯振子,单摆的动力学和共振的关系,力学体系的构成单元是单摆,一个共振对应于一个守恒量,混沌,共振的重叠导致混沌的产生等.我们的出发点是运用二次量子化算子构成的代数哈密顿量,经由海森伯对应而得到的陪集空间上的动力学体系.从此哈密顿量,可以得到动力学势.而动力学势和经典的不动点关系密切,并且量子态就处在由动力学势所包围,分成的几个量子环境中.从动力学势,可以依据它的对称性,方便推得局域模式的存在,最后我们利用这些非线性力学的概念,来分析DCO分子高激发振动态的解离问题.     

Excitation energy transfer mechanisms in allophycocyanin (I)

The mechanisms of excitation energy transfer within allophycocyanin monomer with the theory of generalized master equation (GME) and the technique of time-resobed fluorescence anisotropic spectroscopy are studied. In the case of known information of its structure and spectra, the theory applied is based on the assumption that the coupling interaction between two chromophores is fairly weak. The theory correctly predicts the experimentlly observed rate for excitation energy transfer in allophycocyanin monomer. Based on the results, the energy transfer mechanism can be described as Förster and these processes cannot take place from the high vibrational levels of donor to acceptor.     

Synthesis and energy transfer of model conjugate of phycobilisome rods

The conjugate of R-phycoerythrin (R-PE) and C-phycocyanin (C-PC) was synthesized through a heterobifunctional coupling reagent, N-succinimidyl 3-(2-pyridyldithio) propionate. The molar ratio of R-PE to C-PC was determined by absorption spectra, and the result was 2:1. The energy transfer phenomena were observed from steady-state fluorescence spectra. The calculated result showed that the energy transfer efficiency from R-PE to C-PC was 88%. The energy transfer kinetics was determined by picosecond time-resolved fluorescence spectra. The time constant of energy transfer from R-PE to C-PC was 80 ps, which was much longer than that in the rod of native phycobilisomes.     

用Hammerling交换势计算碱金属原子高激发态能级

 考虑了碱金属原子高激发态价电子与原子实电子coulomb相互作用、交换相互作用以及极化相互作用(长程关联效应),计算了碱金属原子Li,Na,K高激发态(6≤N≤15,l≤2)波函数及能级.计算结果表明:交换势取为GKS势时,能级计算值比实验值偏低;取为hammerling势时,计算值与实验值符合很好.     

Size-reduction of Rydberg collective excited states in cold atomic system

The collective effect of large amounts of atoms exhibit an enhanced interaction between light and atoms. This holds great interest in quantum optics, and quantum information. When a collective excited state of a group of atoms during Rabi oscillation is varying, the oscillation exhibits rich dynamics. Here, we experimentally observe a size-reduction effect of the Rydberg collective state during Rabi oscillation in cold atomic dilute gases. The Rydberg collective state was first created by the Rydberg quantum memory, and we observed a decreased oscillation frequency effect by measuring the time traces of the retrieved light field amplitude, which exhibited chirped characteristics. This is caused by the simultaneous decay to the overall ground state and the overall loss of atoms. The observed oscillations are dependent on the effective Rabi frequency and detuning of the coupling laser, and the dephasing from inhomogeneous broadening. The reported results show the potential prospects of studying the dynamics of the collective effect of a large amount of atoms and manipulating a single-photon wave-packet based on the interaction between light and Rydberg atoms.     

自旋-轨道耦合力对核子最低负宇称态的影响

利用推广的带矢量场的手征SUM夸克模型,计算了核子最低负宇称激发态JP=1/2-,3/2-的能量,分析了各种自旋-轨道耦合势对能量劈裂的影响.结果表明,利用矢量介子场耦合可以改进计算结果,但是能级的次序和实验还是相反的.在此基础上进一步考虑其他的自旋-轨道耦合势,可以给出该激发态正确的能级次序.     

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。     

核子第一正宇称激发态结构的研究

利用几种夸克和手征场耦合模型讨论了核子第一正宇称激发态N*(1440)的结构,分析了各种介子交换效应对能量的影响.结果表明,引入π、σ介子场后可以使激发态能量降低,但比实验值还要高110MeV.在手征SU(3)夸克模型下,由于η,η'和σ'介子提供排斥作用,计算结果增加了50 MeV.最后考虑了矢量介子场耦合,由于ρ介...     

~(69)Ni、~(70)Ni激发态的相对论平均场研究

在球形相对论平均场模型下,采用NL3相互作用,对69N i、70N i基态以及第一、第二激发态进行计算.从核子的半径、价核子的激发能以及中子和质子的密度分布,得出结论:在69N i7、0N i第一和第二激发态都可能存在中子晕现象.     

激发态Cs(6P)原子间碰撞能量转移截面

目的研究Cs(6P3/2)+Cs(6P3/2)→Cs(nLJ=8S1/2,4F5/2,4F7/2)+Cs(6S1/2)碰撞能量合并过程。方法利用一台单模半导体激光器共振激发6P3/2态,利用另一与泵浦激光束反向平行的单模激光束作为吸收线探测激发态原子密度及其空间分布,吸收线调至6P3/2→8S1/2跃迁,并可平行于泵浦激光束移动。由激发态原子密度和谱线的荧光强度比得到碰撞能量合并的截面。结果碰撞转移到8S1/2,4F5/2和4F7/2的截面分别是(5.43±1.56)×10-16cm2,(4.89±1.16)×10-16cm2和(6.17±1.60)×10-16cm2。结论计算结果是准确的并与其它实验结果进行了比较。     

Effects of different aggregation forms of LHC Ⅱ from Bryopsis corticulans on the excited state properties of Chl a

Steady-state and time-resolved fluorescence spectroscopies have been used to study the excited state properties of Chl a in different aggregation forms of light-harvesting complex Ⅱ （LHC Ⅱ） from an intertidal green alga, Bryopsis corticulans, i.e. LHC Ⅱ monomer, trimer and oligomer. When either Chl a or Chl b was selectively excited, the observed decrease in Chl a fluorescence in the oligomer is proved to be caused mainly by the fast fluorescence quenching among Chl a molecules, rather than by the decrease in Chl b-to-Chl a singlet excitation transfer efficiency. Analyses of the picosecond time-resolved fluorescence kinetics identified two exponential decay components in all of the three forms of LHC Ⅱ： a longer-lived component （4.1 -4.7 ns） originating from fluorescence emission of Chl a, and a shorter-lived one （135-540 ps） from the rapid equilibration of singlet excitation among Chl a molecules. The time constant of excitation equilibration is 135 ps in oligomer, 520 ps in trimer and 540 ps in monomer. These results imply that LHC Ⅱ in oligomer form is inherently able to quench Chl a excitation, a mechanism which may be related to the photoprotection of PS Ⅱ via changing the degree of LHC Ⅱ aggregation in Bryopsis corticulans.     

Effects of different aggregatio forms of LHC II from Bryopsis corticulans on the excited state properties of Chl a

Light-harvesting complex II (LHC II) carries out both light harvesting and photoprotection in photosys- tem II (PSII) of higher plant and alga. In light harvest- ing, LHC II absorbs light and efficiently transfers the electronic excitation energy, via inn…     

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。     

Statistical properties for the vibrational energy levels of OCS

A potential energy surface for the electronic ground state of carbonyl sulfide was optimized by using a self-consistent configuration-interaction method and involving the recently observed vibrational band origins up to 8000 cm⁻¹. With the optimized potential, the vibrational energy levels of OCS up to 15000 cm⁻¹ were computed using the discrete variable representation method and Lanczos algorithm. Approximately 480 vibrational energy levels were identified. The statistical investigation showed that the vibrational energy levels of OCS up to 15000 cm⁻¹ are largely regular.