与HBr(Χ~1Σ~+v″=1,J″=12)碰撞的CO_2(00~00)转动态分布

利用受激拉曼泵浦激发HBr分子至Χ~1Σ~+(1,12)激发态,由相干反斯托克斯-拉曼散射(CARS)光谱确定分子的激发.通过测量CARS谱相对强度,得到了HBr分子Χ~1Σ~+态(1,12)能级的布居数密度为n_1=0.54×10~(13) cm~(-3).在一次碰撞条件下,测量碰撞前后CO_2(00~00,J)态的激光感应荧光强度比,得到CO_2转动态的双指数分布.由二分量指数拟合得到T_a=261 K的低能分布和T_b=978 K的高能分布.结果表明,碰撞后约有65%的分子处于低J态,属于弹性或近弹性的弱碰撞;约有35%的分子处于高J态,属于非弹性的强碰撞.在振动-转动平动(V-RT)能量转移过程中,CO_2(00~00,J)态的总出现速率系数为(1.3±0.3)×10~(-10) cm~3 molecule~(-1)s~(-1);低转动态的平均倒空速率系数为(2.9±0.8)×10~(-10) cm~3 molecule~(-1)s~(-1).总的出现速率系数比平均倒空速率系数小,但在量级上保持一致.对CO_2 J=60-74高转动态,随着J值的增加,质心平移温度和质心平移能的平均改变增加.对低转动态,在碰撞过程中,J态既可能出现也可能被倒空,平移能的改变不易确定.     

CO_2与高振动激发K_2碰撞中的全分辨转动态分布

在K_2+CO_2中,受激发射泵浦得到K_2(E=3 500和4 000cm~(-1))高位振动态,研究了高振动激发K_2与CO_2碰撞产生的CO_2全分辨转动态分布。利用高分辨瞬时激光诱导荧光(LIF)测量了CO_2(0000)J=2~74的转动和平移能量轮廓,利用双高斯函数拟合,分别确定各转动态的产生和倒空线宽,从而得到碰撞产生的Doppler展宽、平移温度和平移能。对于K_2不同的激发能E,能量转移的机制是相似的,为振动-转动/平移弛豫机制。但碰撞出现部分的平移温度均超出池温,而碰撞倒空部分的平移温度均略低于池温,平移能随E的增加而增大,E增加14%,平移能增加40%。CO_2(0000)转动态分布的半对数描绘给出了双指数分布,对于K_2E=3 500cm~(-1),低J态分布T_a=(523±60)K,高J态分布T_b=(1 890±210)K。Ta接近池温,说明低J态为近弹性碰撞,属单量子弛豫过程,而高J态为非弹性碰撞,属多量子驰豫过程。对于K_2E=4 000cm~(-1)同样有双指数行为,低J分布T_a=(620±65)K,高J分布T_b=(2 240±250)K。高振动态K_2(E)与CO_2碰撞,E=4 000cm~(-1)比E=3 500cm~(-1)的Ta和Tb均约高19%,说明转动分布对于K_2不同能量是敏感的,但弹性和非弹性分支比是基本相同的,弱碰撞约占82%,强碰撞约占18%。     

CO_2在与高振动激发NaH碰撞中的量子态分辨能量再分配

利用简并受激超拉曼泵浦激发NaH基态到高位振动态(ν″=14,J″=20)。研究了NaH(14,20)与CO_2(00°0)间的振转能量转移。利用吸收系数和瞬时Doppler线宽,得到不同池温下NaH(14,20)分子密度,测量CO_2(00°0,J)与NaH高振动态碰撞前后的瞬时泛频激光感应荧光谱线的相对强度,确定了CO_2(00°0,J=2~80)的初生态布居,它们呈现双指数转动分布。拟合实验数据得到两个转动温度T_(rot)=(650±80)和(1 531±150)K。较冷的分布约占CO_2(00°0)的79%,它是由弹性或弱非弹性碰撞产生的,因而CO_2只有很小的转动激发。另有21%的CO_2(00°0)较大地增加了转动能,故有较热的转动温度。对碰撞产生的CO_2(00°0,J)进行高分辨率瞬时泛频荧光谱线的轮廓测量,得到各转动态平移能的改变。对于CO_2(00°0,J=56~80),转移能从582cm~(-1)(对于J=60)增加到2 973cm~(-1)(对于J=80)。探测转动态布居数的改变,得到各转动态的产生速率系数k_(app)~J之和为(7.2±1.8)×10~(-10) cm~3·mol~(-1)·s~(-1),而平均倒空速率系数〈kdep〉=(6.9±1.7)×10~(-10)cm~3·mol~(-1)·s~(-1)。     

高振动激发K_2与CO_2间弱碰撞和强碰撞的分支比

受激发射泵浦激发K2到X1Σ+g(v″=40,53)振动态.K2(v″)与CO2碰撞,瞬时泛频激光诱导荧光(LIF)测得CO2(0000,J)的初生态布居,其半对数描绘给出了双指数分布.在池温为600 K时,对于v″=40和53,低转动温度T,分别为581±70 K与621±76 K,而高转动温度分别为1395±167 K与1556±187K.T1和T2分别对应于弱碰撞和强碰撞.转动分布对K2(v″)的能量是敏感的,但弱,强碰撞分支比基本相同.利用瞬时泛频LIF强度的相对变化,得到CO2J态的出现和倒空速率系数.确定了CO2平均角动量改变ΔJ和平均反冲速度改变Δvrel间的关系.对于相同角动量的改变,K2(v″)能量增加25%,反冲速度增加约47%.对于K2(v″=40,53)-CO2碰撞,得到了能量转移概率分布函数P(ΔE).     

与HBr(Χ1Σ+ 1,12)碰撞的CO2(0000)转动态分布

摘要：利用受激拉曼泵浦激发HBr分子至Χ1Σ+（1,12）激发态,由相干反斯托克斯-拉曼散射(CARS)光谱确定分子的激发。通过测量CARS谱相对强度,得到了HBr分子Χ1Σ+态（1,12）能级的布居数密度为n1=0.54×1013cm-3。在一次碰撞条件下,测量碰撞前后CO2（0000,J）态的激光感应荧光强度比,得到CO2转动态的双指数分布。由二分量指数拟合得到Ta=261K的低能分布和Tb=978K的高能分布。结果表明,碰撞后约有65%的分子处于低J态,属于弹性或近弹性的弱碰撞;约有35%的分子处于高J态,属于非弹性的强碰撞。在振动-转动平动（V-RT）能量转移过程中,CO2（0000,J）态的总出现速率系数为(1.3±0.3)× 10-10 cm3 molecule-1s-1;低转动态的平均倒空速率系数为(2.9±0.8)×10-10cm3molecule-1s-1。总的出现速率系数比平均倒空速率系数小,但在量级上保持一致。对CO2 J =60-74高转动态,随着J值的增加,质心平移温度和质心平移能的平均改变增加。对低转动态,在碰撞过程中,J态既可能出现也可能被倒空,平移能的改变不易确定。     

高振动激发K2与CO2间弱碰撞和强碰撞的分支比

受激发射泵浦激发K2到X1Σ+g(v″=40,53)振动态。K2(v″)与CO2碰撞,瞬时泛频激光诱导荧光(LIF)测得CO2(0000,J)的初生态布居,其半对数描绘给出了双指数分布。在池温为600K时,对于v″=40和53,低转动温度T,分别为581±70K与621±76K,而高转动温度分别为1395±167K与1556±187K。T1和T2分别对应于弱碰撞和强碰撞。转动分布对K2(v″)的能量是敏感的,但弱,强碰撞分支比基本相同。利用瞬时泛频LIF强度的相对变化,得到CO2 J态的出现和倒空速率系数。确定了CO2平均角动量改变<ΔJ>和平均反冲速度改变<Δʋrel>间的关系。对于相同角动量的改变,K2(v″)能量增加25%,反冲速度增加约47%。对于K2(v″=40,53)- CO2碰撞,得到了能量转移概率分布函数P(ΔE)。     

H对HF泛频激光振转能级粒子数分布的影响

基于多体展式方法所导出的HHF体系的分析势能函数,用准经典的MonteCarlo轨迹法研究了H+HF(v′,J′)→H+HF(v″,J″)振转非弹性碰撞过程。结果表明:H原子对HF在低能和高能范围对高J转动能级有驰豫作用,对HF的振动能级的粒子分布有一定影响     

He和D2分子相互作用转动激发研究

用T.T(K.T.TangandJ.Peter.Toennies)势模型和公认精密度较高的密耦(Close-Coupling)近似方法计算了E=0.1eV和E=0.2eV时,00-00弹性碰撞及00-02、00-04、00-06非弹性碰撞,得出D2分子转动激发分波截面,并得到了原子与分子碰撞弹性分波截面和非弹性激发截面随量子数增加的变化规律.     

He-O2转动激发截面的理论计算

用公认精确的密耦(Close-Coupling)方法、采用两种不同的相互作用势 计算了He-O2碰撞的态-态转动激发截面(E=26.8 meV),通过系统研究和计算发现： 低能散射时,He-O2碰撞的弹性散射主要发生在小角部分,而非弹性转动激发主要发生在 大角部分。研究表明：转动激发截面对势能表面的方向性和散射角都非常敏感。     

H_2(v=1)与CO_2碰撞中CO_2的振动和转动激发

利用高分辨率瞬时激光光谱技术,研究了H2(1,1)与CO2碰撞中的能量转移。受激拉曼泵浦把H2(0,1)激发到H2(1,1)能级,H2(1,1)与CO2碰撞,使CO2的振转态得到布居,通过泛频吸收得到CO2(0000)和(0001)的转动态分布,测量H2(0,1)和H2(1,1)的CARS(相干反斯托克斯拉曼散射)谱,得到这二个能级布居数密度之比,而H2(0,1)密度通过在池温300K下H2(v=0)的转动Boltzmann分布得到。碰撞转移速率系数由一个速率方程得到,对于CO2(0000)J=48~76,速率系数ktr从(3.9±0.8)×10-11单调递增到(1.4±0.3)×10-10 cm3·molecule-1·s-1,而对于(0001)J=5~33,速率系数均在(4.3±0.9)×10-12cm3·molecule-1·s-1附近。随H2(1,1)的激发,在0.5μs内测量CO2(0000)和(0001)原生态的转动布居,得到玻尔兹曼转动温度Trot,对于(0000)态,有Trot=1 100K,对于(0001)态有Trot=310K,与池温接近。利用泛频吸收线的多普勒增宽测量,得到CO2各转动态的实验室平移温度Ttran和质心平移温度Trel,对于(0000)J=48和76,Trel分别为454和1 532K,平动能平均变化在231~1 848cm-1之间,而对于(0001)J=5~33,平均平动能基本无变化。     

Broadening of a two-photon resonance in a zinc atom in collisions with CO<Subscript>2</Subscript>, CO,and NO molecules

The broadening of a two-photon resonance is studied experimentally at the 4s¹S₀?6s³S₁ transition in a zinc atom upon absorption of two waves with a small detuning from an intermediate state in collisions with CO₂, CO, and NO molecules. The measured absolute values of broadening cross sections greatly exceed gas-kinetic cross sections and are (9.4±2.4, 6.5±1.6, and 3.9±1.0)×10^{? 14}cm² for CO², CO, and NO, respectively. Anomalously large rate constants and cross sections obtained in experiments are explained by the efficient resonance quenching of the excited states of zinc atoms in collisions with molecules accompanied by transfer of the energy of excited atoms to vibrational-rotational degrees of freedom of molecules.     

Diode laser study of IR multiphoton-induced depletion of rotational sublevels of the ground vibrational state of SF6 molecules cooled in a pulsed free jet

A pulsed frequency tunable diode laser was used to investigate the IR multiphoton-induced depletion of rotational sublevels of the ground vibrational state of SF₆ molecules cooled in a pulsed free jet at exciting energy densities between ≈10^-2 and 2.3 J cm^-2. The depletion of all rotational sublevels was effective at considerable (≈5–11 cm^-1) pumping frequency detunings from the linear absorption spectrum (LAS) of the molecule the width of which under the conditions of experiment (T_rot ≈ 18 K) was ≈2–3 cm^-1. The fraction of molecules excited by a pumping pulse from individual rotational sublevels was measured and its dependence on the exciting pulse frequency and energy density investigated. The effect of collisions on the depletion of the rotational sublevels was studied.     

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。     

CO三重带系d3Δ-a3Π(4,0)和(5,0)带激光光谱研究

光外差磁旋转浓度调制激光光谱技术属于一种高灵敏度的吸收光谱测量方法 ,可以用于瞬态分子和激发态分子光谱的检测。采用这种技术分别在 16 4 0 0～ 16 6 5 0cm-1和 174 5 0～ 1775 0cm-1波段内直接观测到CO三重带系d3 Δ←a3 Π(4,0 ) (5 ,0 )振转吸收光谱。这种跃迁的上态d3 Δ1(v =4 ) ,d3 Δ2 (v =4 ) ,d3 Δ1(v =5 )分别与A1Π(v =0 ) ,D1Δ(v =0 )和A1Π(v =1)态存在微扰相互作用。通过对所测量到的 CO三重带系 (4,0 ) (5 ,0 )振转谱带作了包含微扰相互作用在内的分析 ,获得了上态d3 Δ(v =4 ,5 )的精确的分子转动光谱常数。     

H-atom abstraction dynamics of reactions between Cl atoms and heterocyclic organic molecules

The HCl(v' = 0, J') rotational state distributions produced in the photoinitiated reactions of ground spin-orbit state Cl(2P3/2) atoms with the organic heterocycles oxirane (c-C2H4O), thiirane (c-C2H4S) and oxetane (c-C3H6O) have been measured using the technique of 2 + 1 resonance-enhanced multiphoton ionization in a time-of-flight mass spectrometer. In contrast to previous studies of H-atom abstraction dynamics by Cl atoms with linear functionalized molecules, the nascent HCl(v' = 0, J') products of the reactions of the three-membered heterocycles oxirane and thiirane are formed rotationally cold, with mean rotational energies <Erot> of (0.28 ± 0.02) kcal mol-1 and (0.31 ± 0.02) kcal mol-1, respectively. The reaction of Cl atoms with the four-membered heterocycle oxetane, however, results in more rotationally excited HCl(v' = 0, J') products for which <Erot> = (0.78 ± 0.03) kcal mol-1. Ab initio calculations were performed at the G2//MP2/6-311G(d,p) level to characterize molecular complexes and transition states on the reactive pathways. In all cases, the reactions were calculated to be barrierless, and weakly bound pre- and post-reaction complexes were located on the potential energy surfaces. The observed distributions and calculated reaction profiles are compared with previous studies of the reactions of Cl atoms with linear functionalized organic molecules and the consequences of the constrained molecular geometry on the HCl(v' = 0, J') rotational distribution discussed in terms of the dipole-dipole interaction model proposed previously.     

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%。     

Population redistribution in optically trapped polar molecules

We investigate the rovibrational population redistribution of polar molecules in the electronic ground state induced by spontaneous emission and blackbody radiation. As a model system we use optically trapped LiCs molecules formed by photoassociation in an ultracold two-species gas. The population dynamics of vibrational and rotational states is modeled using an ab initio electric dipole moment function and experimental potential energy curves. Comparison with the evolution of the v″ = 3 electronic ground state yields good qualitative agreement. The analysis provides important input to assess applications of ultracold LiCs molecules in quantum simulation and ultracold chemistry.     

Formation of ultracold polar molecules in the rovibrational ground state

Ultracold LiCs molecules in the absolute ground state X1Sigma+, v' = 0, J' = 0 are formed via a single photoassociation step starting from laser-cooled atoms. The selective production of v' = 0, J' = 2 molecules with a 50-fold higher rate is also demonstrated. The rotational and vibrational state of the ground state molecules is determined in a setup combining depletion spectroscopy with resonant-enhanced multiphoton ionization time-of-flight spectroscopy. Using the determined production rate of up to 5 x 10(3) molecules/s, we describe a simple scheme which can provide large samples of externally and internally cold dipolar molecules.