激发态Cs2和H2的电子-振转能级的碰撞转移

利用相干反斯托克斯拉曼光谱(CARS)探测技术, 研究了激发态Cs2与H2间的电子-振转能级的碰撞转移。用波长为532 nm和中心波长为716 nm的两束激光同时聚焦到样品池中, 扫描CARS谱确认了H2分子的S支(△v =1, △J=2)仅在v=1, J=4,5及v=2, J=3,4能级上有布居, 用n1、n2、n3、n4分别表示(2,4)、(2,3)、(1,4)及(1,5)上的粒子数密度。从CARS线的峰值得到n2/n1、n3/n1、n4/n1分别为6.34±1.27、3.66±0.73和1.45±0.29。转移能配置到振动、转动和平动的比例分别为0.44、0.06和0.50, 能量主要分配在振动和平动上。在T=523 K和PH2=2.5×103 Pa条件下, 通过求解速率方程组和对时间分辨CARS线轮廓的分析, 得到碰撞转移速率系数k1=(6.0±1.2)×10-14 cm-3s-1和k2=(4.0±0.8)×10-13cm-3 s-1。     

H2(v=3)+H2(He)碰撞中的转动能量转移

激发态Na2与H2碰撞,使H2(v=3,J=3)得到布居,在H2和He总气压为800Pa及温度为700K的条件下,利用相干反斯托克斯拉曼散射（CARS）光谱技术研究了H2(3,3)与H2(He)间转动能量转移过程。改变CARS激光束与激发Na2的激光之间的延迟时间,测量He不同摩尔配比时H2(3,J)态CARS谱强度的时间演化,得到H2(3,3)的总弛豫速率系数分别为=(21±5)×10-13cm3s-1和=(5.6±1.6)×10-13cm3s-1。测量H2(3,J)各转动态的相对CARS谱强度,由速率方程分析,得到H2(3,3)+H2→H2(3,J)+H2中,对于J=2,4,转移速率系数分别为11±4和8.2±3.1cm3s-1。在H2(3,3)+He→H2(3,J)+He中,对于J=2,4,转移速率系数分别为3.1±1.2和2.1±0.7cm3s-1。对于H2(3,3),单量子弛豫׀∆J׀=1约占该态总弛豫率的90%。     

K分子高激发振动能级 （V=46-61）与H分子间的碰撞能量转移

利用相干反斯托克斯拉曼光谱（CARS）探测技术,研究了K2的 （V=46-61）与H2间的电子-振转动能级的碰撞转移,扫描CARS谱确认了仅在H2的V=2,J=0,1,2及V=1,J=2能级上有布居,用n1,n2,n3,n4,分别表示(2,0) ,(2,1) ,(2,2) ,(1,2）上的粒子数密度,从CARS谱峰值得到n1／n4,n2／n4,n3／n4 分别为3.3±0.5,2.2±0.3,2.0±0.3,有88%粒子处在V=2能级上,而在V=1能级上有12%。转移能配置到振动,转动,平动的比例分别为0.53,0.01,0.46,能量主要分配在振动和平动上,在573K和5×103 Pa条件下,通过求解速率方程组和对时间分辨CARS线强度分析得到碰撞转移速率系数k12=(3.3±0.7) ×10-14 cm3s-1和k2=（1.4±0.3）×10-14cm3s-1。     

K分子高激发振动能级 （V=46-61）与H分子间的碰撞能量转移

利用相干反斯托克斯拉曼光谱（CARS）探测技术,研究了K2的 （V=46-61）与H2间的电子-振转动能级的碰撞转移,扫描CARS谱确认了仅在H2的V=2,J=0,1,2及V=1,J=2能级上有布居,用n1,n2,n3,n4,分别表示(2,0) ,(2,1) ,(2,2) ,(1,2）上的粒子数密度,从CARS谱峰值得到n1／n4,n2／n4,n3／n4 分别为3.3±0.5,2.2±0.3,2.0±0.3,有88%粒子处在V=2能级上,而在V=1能级上有12%。转移能配置到振动,转动,平动的比例分别为0.53,0.01,0.46,能量主要分配在振动和平动上,在573K和5×103 Pa条件下,通过求解速率方程组和对时间分辨CARS线强度分析得到碰撞转移速率系数k12=(3.3±0.7) ×10-14 cm3s-1和k2=（1.4±0.3）×10-14cm3s-1。     

Cs(6D5/2)+H2→CsH[ X1Σ+(v,J)]+H转动分辨总截面的测量

利用泵浦-检测方法,在样品池条件下,研究了Cs(6D5/2)与H2反应碰撞传能过程。利用激光感应荧光（LIF）光谱技术,确定了CsH[X1Σ+(v,J)]振转能级上的布居分布,转动态分布与热统计分布基本一致.Cs激发态原子密度由激光能量吸收得到.记录A1Σ+(v',J+1)→X1Σ+(v,J)的时间分辨荧光,从荧光强度的对数值给出的直线斜率确定(v',J+1)→(v,J)的自然辐射率,结合(v,J)→(v',J+1)吸收系数的测量,得到反应生成物CsH[X1Σ+(v,J)]态的分子密度.由速率方程分析,给出反应截面(v,J),对J求和,得到(v)[10-16cm2单位]分别为（0.64±0.19）（v=0）和（0.58±0.17）（v=1）.     

Cs(6D5/2)+H2→CsH[X1∑+(v,J)]+H转动分辨总截面的测量

利用泵浦-检测方法,在样品池条件下,研究了Cs(6D5/2)与H2反应碰撞传能过程.利用激光感应荧光(LIF)光谱技术,确定了CsH[X1∑+(v,J)]振转能级上的布居分布,转动态分布与热统计分布基本一致.Cs激发态原子密度由激光能量吸收得到.记录A1∑+(v',J+1)→X1∑+(v,J)的时间分辨荧光,从荧光强度的对数值给出的直线斜率确定(v',J+1)→(v,J)的自然辐射率,结合(v,J)→(v',J+1)吸收系数的测量,得到反应生成物CsH[x1∑+(v,J)]态的分子密度.由速率方程分析,给出反应截面σ(v,J),对J求和,得到σ(v)[10-16 cm2单位]分别为(0.64士0.19)(v=0)和(0.58士0.17)(v=1).     

高位振动态RbH(Х1Σ+,v″≧15) 与CO2碰撞转移中的能量相关性

研究了高位振动态RbH(Х1Σ+,v″=15-21)与CO2碰撞转移过程。脉冲激光激发RbH至高位态,利用激光感应荧光 光谱(LIF)得到RbH(Х1Σ+,v″)与CO2的猝灭速率系数,。利用激光泛频光谱技术,测量了CO2(0000,J)高转动态分布。得到了转动温度,从而获得了平均转动能和转动能的变化<ΔErot>,发现。对于v"=16,证实了振动—振动能量转移的4-1近共振过程。在一次碰撞条件下,通过速率方程分析,得到RH(v")-CO2振转速率系数。对于v"=15,J=32-48,速率系数在1.25-0.33×10-13cm3s-1.之间,对于v"=21,速率系数在2.47-1. 53×10-13cm3s-1之间,其能量相关性是明显的。     

反应物转动激发对F+H2→HF+H体系反应动力学的影响

利用高分辨的交叉分子束装置研究了F+H₂(v=0,j=0, 1)反应在碰撞能1.27 kcal/mol下的动力学行为, 获得了产物HF(v′=1,2,3)转动态分辨的微分散射截面．当反应物H₂ 处于不同转动量子态j=0和1时,产物HF(v′=2)的散射角分布都主要表现为后向散射,但HF(v′=2)的转动态布居与反应物的转动量子态密切相关,转动激发的H₂分子将产生转动“更热”的HF(v′=2) 产物．另外,对于HF(v′=3)产物通道,由于slow-down机理的影响,当H₂布居于j=0时前向散射表现更显著．     

H2（V=3）+H2（He）碰撞中的转动能量转移

激发态Na₂与H₂碰撞,使H₂（V=3,J=3）得到布居,在H₂和He总气压为800 Pa及温度为700 K的条件下,利用相干反斯托克斯拉曼散射（CARS）光谱技术研究了H₂（3,3）与H₂（He）间转动能量转移过程.改变CARS激光束与激发Na₂的激光之间的延迟时间,测量He不同摩尔配比时H₂（3,J）态CARS谱强度的时间演化,得到H₂（3,3）的总弛豫速率系数分别为k_3,3^H₂=（21士5）×10^-3cm³·s^-1和k_3,3^H_e=（5.6士1.6）×10^-13cm³·s^-1.测量H₂（3,J）各转动态的相对CARS谱强度,由速率方程分析,得到H₂（3,3）+H₂→H₂（3,J）+H₂中,对于J=2,4,转移速率系数分别为（11±4）×10^-13cm³·s^-1和（8.2±3.1）×10^-13cm³·s_<sup>-1.在H₂（3,3）+He→H₂（3,J）+He中,对于J=2,4,转移速率系数分别为（3.1±1.2）×10^-13cm³·s^-1和（2.1士0.7）×10¹³cm³·s^-1.对于H₂（3,3）,单量子弛豫|△J|=1约占该态总弛豫率的90%.     

碱性成纤维细胞生长因子对PC12细胞氧化损伤的保护作用和机制

探讨碱性成纤维细胞生长因子(bFGF)对H<,2>O<,2>诱导PC12细胞凋亡的影响及其作用机制.利用H<,2>O<,2>诱导的PC12细胞建立细胞氧化损伤模型,用不同浓度的bFGF进行药物干预,CCK-8法和流式细胞技术检测细胞存活率和凋亡率,试剂盒测定超氧化物歧化酶(SOD)活性,Western blot检测ER...     

激发态H2(X1∑+g,v=1,J=1)之间的碰撞能量合并

受激拉曼激发H2(0,1)基态的Q支得到H2(1,1)能级.在室温条件下,利用反斯托克斯拉曼散射(CARS)探测技术测量了碰撞能量合并(EP)过程H2(1,1)+H2(1,1)→H2(2,J)+H2(0,J″)及H2(1,1)与H2(1,J)转动能级间的碰撞转移速率系数.扫描CARS谱表明在H2(1,1)能级的碰撞能量...     

K_2(9~1∑~+_g)高位电子态与H_2碰撞中H_2的能量分布

光学-光学双共振激发K2到91∑+g高位态,研究了K2(91∑+g)与H2的电子-振转碰撞能量转移。利用相干反斯托克斯(CARS)光谱技术探测H2的振转态分布,扫描CARS谱表明H2在(1,1)、(2,1)、(2,2)、(3,1)、(3,2)、(3,3)和(3,5)能级上有布居。由时间分辨CARS轮廓得到H2各振转能级上粒子数之比,得到H2的平均振动能和平均转动能分别为9063cm-1和388cm-1。从91∑+g→11∑+u、11∑+u→11∑+g、33∏g→13∑+u跃迁的时间分辨激光感应荧光(LIF)强度得到它们的自发辐射率和碰撞转移率。在H2压强为3×103Pa时,K2(91∑+g)与H2的碰撞转移能为16930cm-1。H2的平均振转能占平均转移能的56%。     

NaK(61Σ+)与H2碰撞传能中的H2的振转态分布

光学-光学双共振激发NaK至61Σ+高位电子态,研究了NaK(61Σ+)与H₂的电子-振转能量转移。利用相干反斯托克斯拉曼散射(CARS)光谱技术检测H₂的振转态分布。扫描CARS谱表明H₂在(1,1),(2,1),(2,2),(2,3),(3,1),(3,2),(3,3)和(3,5)振转能级上有布居。对于(3,1), (3,2), (3,3)和(3,5)能级,扫描CARS谱峰值直接给出布居数之比。对于(1,1), (2,1), (2,2)和(2,3)能级,扫描CARS谱峰值给出二个可能的布居数之比,利用一个速率方程组,由时间分辨CARS轮廓可以得到真实的比值。用n₁～n₈分别表示H₂的(3,1), (2,1), (1,1), (3,3), (2,3), (2,2), (3,2)和(3,5)能级上布居密度,得到n₂/n₁～n₈/n₁分别为0.51,0.97,0.45,0.18,0.10,0.26和0.31。利用Stern-Volmer公式,得到61Σ+态的总退布速率系数为(2.1±0.4)×10-10 cm3s-1, 由H₂各振转能级布居数之比,得到61Σ+-(1,1), (2,1), (2,2), (2,3), (3,1), (3,2), (3,3)和(3,5)转移速率系数(10-11 cm3·s-1单位)分别为5.4±1.6,2.8±0.8,0.6±0.2,1.0±0.3,5.6±1.7,1.4±0.4,2.5±0.8和1.7±0.5。     

Collision-induced vibrational energy transfer: K2[1(1) sigmau+ (nu'=2)]+He, H2-->K2[1(1) sigmau+(nu'=1,3)]+He, H2

Collisional energy transfer processes K2[1(1) sigmau+ (nu'=2)]+He, H2-->K2[1(1) sigmau+(nu'=1,3)]+He, H2 were studied by laser induced fluorescence under gas cell conditions. During the experiments, the cell temperature was kept constant at 420K. The buffer gas pressure was varied over the range from 40 to 250 Pa, Kz molecules were irradiated with pulses of radiation from an OPO laser, populating K2[1(1) sigmau+ (nu'=2)] by photon absorption. The resulting fluorescence included the direct component emitted in the decay of the optically excited state and the sensitized components arising from collisionally populated states. The decay signal of time-resolved fluorescence from 1(1) sigmau+ (nu'=2)]-->1(1) sigmag+(nu"=0) transition was monitored. In the early period after excitation, only very little population in states v'= 1 or 3 had yet accumulated, the rate of collisional activation to the state nu'=2 was negligible. The decay curve of the nu' = 2-->nu" = 0 was treated as a single exponential function. From the measurement of the time-resolved fluorescence, the semilog plot was shown. The slope yielded the effective lifetime of the nu' = 2--> nu' = 0 transition. Based on the Stern-Volmer equation, the radiative lifetime (36 +/- 7) ns was obtained. The total cross sections for deactivation of 1(1) sigmau1 (nu'=2) state by means of collisions with He and H2 are (3.0 +/- 0.5) x 10(-16) cm2 and (6.4 +/- 1.2) x 10(-15) cm2, respectively. The radiative lifetimes of 1(1) sigmau+(nu' = 1,3) states can also be determined through time-resolved fluorescence in pure K vapor. The time-integrated intensities of 1(1)sigmau+(nu' = 1,2,3)-->1(1) sigmag+(nu"=0) transition at different He or Hz pressure were measured. The ratio of fluorescence intensities versus 1/P(He, H2) can be fitted by a straight line. The slopes yield the cross sections sigma(nu'=2-->nu'=1) = (1.4 +/- 0.5) x 10(-16) cm2 and (3.2 +/- 1.0) x 10(-15) cm2; sigma(nu'=2-->nu'=3)= (1.2 +/- 0.4) x 10(-16) cm2 and (2.6 +/- 0.9) x 10(-15) cm2 for He and H2, respectively. Cross sections for the effective quenching of the nu' = 1,2,3 states were also determined. To our knowledge, the cross-sections for these processes are reported for first time.     

Rb(5PJ)与He,N2的碰撞精细结构混合和猝灭

在气体样品池条件下,研究了Rb(5PJ) (He,N2)碰撞能量转移过程.用调频半导体激光器激发Rb原子至Rb(5P3/2)态,在不同的He或N2气压下,测量了直接5P3/2→5S1/2荧光和转移5P1/2→5S1/2荧光.对于Rb(5PJ)与He的碰撞,只发生精细结构转移(略去碰撞猝灭效应),电子态能量仅能转移为He原子的平动能.在与N2的碰撞中,向分子振转态的转移是重要的.本实验中,Rb的密度为4.5×1011 cm-3,由辐射陷获理论得到5P1/2→5S1/2的有效辐射率为2.47×107 s-1.利用速率方程分析,可以得到碰撞转移速率系数,对于He,5P3/2→5S1/2转移速率系数kHe21=2.61×10 12 cm3·s.对于N2,测量5PJ He和5PJ N2两种情况下直接荧光与敏化荧光的相对强度比,利用最小二乘法确定5Pa/2→5S1/2转移速率系数kN212=2.36×10-11 cm3·s,5PJ态猝灭速率系数kN2=1.44×10-11 cm3·s-1.由实验结果证实了Cs-N2主要是直线式碰撞传能机制,与其他实验结果进行了比较.     

H(2)-Broadening Coefficients in the nu(4) Band of NH(3)

H(2)-broadening coefficients have been measured for 66 rovibrational lines of NH(3) at room temperature in the (P)P and (R)P branches of the nu(4) band in the range 1470-1600 cm(-1), using a high-resolution Fourier transform spectrometer. The collisional widths are obtained by fitting Voigt profiles to the measured shapes of the lines. The broadening coefficients are found to decrease on the whole as J increases and they increase with K for a given J value. The results are compared with those calculated from a semiclassical model in which the inversion vibration of NH(3) and collision-induced transitions with DeltaK = 0 and DeltaK = +/- 3 are taken into account. The intermolecular potential used includes electrostatic, induction, and dispersion energy contributions. The calculations performed by considering only DeltaK = 0 transitions provide significantly lower broadenings but with a satisfactory J and K dependence. The same trends are obtained for the broadening coefficients in inversion-rotation transitions and in the Q branch of the nu(1) parallel band of NH(3). Copyright 2001 Academic Press.     

Experimental Characterization of the Higher Vibrationally Excited States of HCO(+): Determination of omega(2), x(22), g(22), and B(030)

Analyses of high Rydberg series of HCO converging to the (030) vibrational state of the cation establish rovibrational state-detailed thresholds for HCO(+). UV-visible laser double resonance isolates series for assignment. Strongly vertical Rydberg-Rydberg transitions from photoselected N' = 0 and N' = 2 rotational levels of the Sigma(-) Renner-Teller vibronic component of the 3ppi (2)Pi (030) complex define individual series converging to rotational levels, N(+) = 1 through 5 and 3 through 5 of the HCO(+) vibrational states (03(1)0) and (03(3)0), respectively. Extrapolation of autoionizing series locates the positions of these rovibrational states to within +/-0.01 cm(-1). The use of this information combined with precise ionization limits for lower vibrational states determined from earlier Rydberg extrapolations and spectroscopic information available from infrared absorption measurements enables an estimate of the force-field parameters for HCO(+) bending. These parameters include the harmonic bending frequency, omega(2) = 842.57 cm(-1), the vibrational angular momentum splitting constant, g(22) = 3.26 cm(-1), and the diagonal bending anharmonicity, x(22) = -2.53 cm(-1), separated from the off-diagonal contribution, x(12), by reference to ab initio calculations. Results of experiment on the higher vibrationally excited states of HCO(+) are compared with recent theoretical predictions. Copyright 2000 Academic Press.     

紫色光合细菌中类胡萝卜素的选择性分布及功能

紫色光合细菌Rhodopseudomonas (Rps.) palustris光合膜中的外周捕光天线(LH2)及核心复合物(LH1-RC)中都含有多种类胡萝卜素分子(Crt)。研究不同种类的Crt在上述色素蛋白复合物中的分布及其生理学功能具有重要意义。采用了高效液相色谱(HPLC)手段分析了中等光强(～4 000 lux)培养条件下所获得的Rps. palustris的LH2及LH1-RC中的Crt组成,发现共轭双键数目(n)为11或12的类胡萝卜素分子(包括lycopene(n=11),Anhydrorhodivibrin(n=12)及Rhodopin(n=12)等,主要集中在LH2复合物中,而n=13的类胡萝卜素分子Spirilloxanthin则优先结合到LH1-RC中。通过将稳态吸收光谱及近红外荧光激发光谱在细菌叶绿素的Qx带处归一化,并比较两者的数值,发现在LH2中Crt从单重态向BChl的传能效率［30.9%(v=0),25.4%(v=1),30.4%(v=2)］明显高于在LH1-RC中的传能效率［10.7%(v=0),7.8%(v=1),11.4%(v=2)］。此外,本文还运用亚微秒时间分辨吸收光谱检测了类胡萝卜素三重态T_n←T₁吸收,发现伴随着532 nm激光脉冲激发,LH1-RC和LH2中Crt三重态的吸收主峰位于571及560 nm左右,它们分别归属于n=13和n=12的类胡萝卜素分子。通过对动力学衰减曲线进行单指数拟合,发现前者的衰减时间常数(1.6 μs)明显短于后者(2.2 μs)。上述研究结果表明,短链Crt易于结合到LH2中承担捕光的功能,而长链Crt优先结合到LH1-RC中发挥光保护功能。     

利用光学-光学双共振研究谱线的碰撞增宽

利用光学-光学双共振光谱技术研究了NaK分子21Σ＋→６1Σ＋跃迁线的碰撞增宽。一台单模半导体激光器实现11Σ＋(v″,J″)→21Σ＋(v′,J′)的跃迁,另一单模半导体激光器激发21Σ＋(v′,J′)能级到６1Σ＋的振转能级,二激光束反向平行通过样品池。谱线总线宽与K原子密度成线性关系,由其斜率得到增宽速率系数k_br＝(1.4±0.7)×10-8 cm3·s-1。同时研究了21Σ＋(v＝8,J＝12)→21Σ＋(v＝8,J＝13,14)转动能级间的碰撞激发转移,测量谱线的相对强度,由速率方程得到碰撞转移速率分别为6.1×106和5.2×106 s-1。