高振动激发LiCs与CO_2碰撞中的振动-转动能量转移

受激发射泵浦得到的LiCs高位振动态与CO_2碰撞,研究了LiCs不同能量对碰撞能量转移过程的影响.利用高分辨率瞬时激光感应荧光(LIF)测量得到CO_2(0000,J=2-74)原生转动态分布.转动布居数的半对数描绘给出了一个双指数结构,得到了一个T_a=660±73K[对LiCs(E=4300cm~(-1))]和550±61K[对LiCs(E=3700cm~(-1))]的低能分布,一个T_b=2380±261K[对LiCs(E=4300cm~(-1))]和1980±217K[对LiCs(E=3700cm~(-1))]的高能分布,低能分布属于弹性或弱非弹性碰撞,高能分布属于强非弹性碰撞.转动分布对LiCs能量是敏感的.但弹性与非弹性分支比基本是相同的.在一次碰撞的条件下,测量了各J态的出现和倒空速率系数,它们仅弱依赖于LiCs激发能.出现和倒空速率系数对不同LiCs能量基本一致,是振动-转动/平移弛豫轨道的重要证据.     

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)。     

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。     

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).     

CsH(X1∑+,v≥15)与CO2碰撞中的振动-转动能量转移

研究了高位振动激发态CsH(v"=15～21)与CO2振动-转动碰撞转移过程.脉冲激光激发CsH至高振动态,利用激光感生荧光光谱(LIF)得到CsH(v")与CO2的猝灭速率系数kv"(CO2),kv"＝21(CO2)＝7kv"＝15(CO2).研究了CsH(v")+H2的弛豫过程,有kv"(H2)＞kv"(CQ),碰撞弛豫速率系数的质量效应明显.利用激光泛频光谱技术,测量了CO2(00°0)的转动态分布.对于CO2与CsH(v"=15)碰撞,CQ2有转动温度Trot=(605±50)K;对于v"=21,Trot=(780±70)K.基于转动温度,得到CO2的平均转动能〈Erot〉和转动能的变化〈ΔErot〉,发现〈ΔErot〉v"=21～2.7〈△Erot〉v"=15.由对CO2转动能级受激吸收线轮廓测量,得到J=36～48各能级的平均平动能〈Etel〉,对于v"＝15,〈Erel〉＝600～972 cm-1;对于v"=21,〈Erel〉=972～1351cm-1.低J值有低平动能.外推平动能到初始平动能520 cm-1(池温500 K的平动能)对于v"＝15和v"＝21,分别得到阈值Jth =34和24.大于初始平动能的转动态均处于Jth值之上.     

K_2(~1∧_g)高位态的预解离和碰撞转移

利用光学双共振和激光光谱技术,测量了K_2(~1A_g)态的预解离率和碰撞转移率.脉冲激光将K_2(1~1∑_g~+)基态激发至1~1∑_u~+态,由连续激光激发1~1∑_u~+至激高位~1A_g态.在不同K密度下,记录~1A_g→~1A_u跃迁的时间分辨荧光,光强的对数与衰变时间成线性关系,从直线的斜率得到~1A_g态的有效寿命,由Stern-Volmer方程得到~1A_g态的辐射率与预解离率之和及总的碰撞去布居截面.在不同的K密度下测量时间积分荧光强度I_3[K_2(~1A_g)→K_2(~1A_u)],I_2[K(6S)→K(4P_(3/2))]和I_1[K(4D)→K(4P_(3/2))],光强比I_1/I_3和I_2/I_3与K密度也成线性关系.从直线的斜率和截距并结合从Stern-Volmer方程得到的结果,确定K_3(~1A_g)的预解离率Γ_(P6S)=(1.2±0.4)×10~7s~(-1),Γ_(P4D)=(0.8±0.3)×10~7s~(-1)和碰撞转移截面σss=(1.9±0.6)×10~(-14)cm~2,σ_(4D)=(9.0±3.0)×10~(-15)cm~2.     

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)。     

Cs(6 ~2D_(5/2))与H_2反应生成的CsH分子的转动和振动态分布

利用激光泵浦-探测技术,在样品池条件下,研究了Cs(6D5/2)态与H2反应生成的CsH分子基电子态的转动和振动的量子态分布。在Cs-H2混合蒸气中,脉冲激光双光子激发Cs(6D5/2)态,另一台调频脉冲激光器扫描CsHX1Σ+(v″,J″)→A1Σ+(v′,J′=J″±1)吸收线,发现CsH分子只有v″=0和1上的振动带上有布居而不布居在v″1的振动带上。v″=0和1上的转动带分布呈现单峰结构,其峰值位于J″=6～8处,转动带分布轮廓与池温下的统计分布接近。转动Boltzmann温度分别为(458±20)K(对v″=1)和(447±18)K(对v″=0),得到的CsH分子的转动温度稍低于池温。从转动态分布得到v″=1与v″=0上布居数之比约为0.897,从而计算出CsH基电子态上的平均转动能ER和平均振动能EV,有效能减去平均振转能得到平均平动能ET。CsH分子3种能量的相对比值fT∶fV∶     

Scattering of N2 from Ni(111)

A cold (T_rot<10 K) beam of N₂ with an initial translational energy of 0.40 eV strikes an Ni(111) surface at surface temperatures from 300 to 873 K at several incident angles from 15 to 60°. The rotational energy and angular distributions of the scattered molecules are probed using (2+1) resonance-enhanced multiphoton ionization. Molecules scattered in the specular direction have mean rotational energies that are independent of surface temperature, whereas those scattered at angles far from the specular show a dependence on surface temperature, caused likely by multiple collisions with the surface before escape. A rotational rainbow, seen in systems such as CO–Ni(111) and N₂–Ag(111), is not seen in this system. For molecules that scatter close to the specular direction, approximately 10% of the initial translational energy is converted into rotational energy of the scattered N₂. For surface temperatures above room temperature, the angular distributions indicate that molecules that scatter into low-J states also tend to exit in a broad peak (10–20° FWHM) near the specular, and this peak is broadened with increasing incident angle. The molecules that scatter into high-J states have a much broader distribution, indicating that they are trapped rotationally during the initial collision and suffer multiple collisions before leaving the surface.     

Scattering of CO and N(2) molecules by a graphite surface

Measurements of angular distributions for the scattering of well-defined incident beams of CO and N(2) molecules from a graphite surface are presented. The measurements were carried out over a range of graphite surface temperatures from 150 to 400?K and a range of incident translational energies from 275 to over 600?meV. The behavior of the widths, positions and relative intensities of the angular distributions for both CO and N(2) were found to be quite similar. The experimental measurements are discussed in comparison with calculations using a classical mechanical model that describes single collisions with a surface. Based on the behavior of the angular distributions as functions of temperature and incident translational energy, and the agreement between measured data and calculations of the single-collision model, it is concluded that the scattering process is predominantly a single collision with a collective surface for which the effective mass is significantly larger than that of a single carbon atom. This conclusion is consistent with that of earlier experiments for molecular beams of O(2) molecules and Xe atoms scattering from graphite. Further calculations are carried out with the theoretical molecular scattering model in order to predict translational and rotational energy transfers to and from the molecule during scattering events under similar initial conditions.     

Scattering of NO from a graphite surface at cryogenic temperatures

The scattering of NO molecules from a graphite surface at cryogenic temperatures (T_s<80 K) allows to study the molecular translation-rotation energy transfer without surface phonon contributions in the entrance channel. The angular distributions show that there are no diffusely scattered molecules at surface temperatures below T_s=70 K, whereas the signal of forward scattered molecules remains present down to T_s=20 K, the lowest temperature investigated. The rotational behavior of the scattered molecules can be described by a Boltzmann distribution characterized by a rotational temperature T_rot. It is nearly constant below T_s=80 K and is determined by the molecular kinetic energy in surface normal direction. The data are consistent with the formation of a short-lived collision complex (NO··C_n) between the NO molecule and a few surface atoms. The complex decomposes in a unimolecular fashion. The cryogenic surface temperatures require effective shielding of the crystal from the heat radiation of the surrounding experimental equipment. The data show that the heat radiation influences the crystal temperature, however, it has only negligible influence on the molecule–surface interaction.     

双甘氨肽与高定向热解石墨的散射动力学研究

本文通过反应力场来研究中性双甘氨肽与高取向热解石墨的碰撞动力学过程,分别模拟初始入射角度为0o、20o、45o和70o以及入射能量为481.5 kJ/mol和表面温度为677 K的情况,并且确定和分析了散射产物的角度分布、平动能分布、内能分布和表面滞留时间分布. 双甘氨肽是一种多原子分子,具有较多的低频振动模式和较强的表面吸附相互作用,这些使得碰撞过程的表面滞留时间较长和容易造成能量损失,尤其是表面法线方向. 由于碰撞分子的动量沿表面法线方向上明显地发生损失,而沿表面平行方向上的动量则会大部分保留,因此,其散射角通常会呈现出超镜面反射分布,并且末态的平动能要远小于所谓硬立方模型的预测值. 本文加深了多肽分子与高取向热解石墨碰撞及其能量转移过程的认识和理解,有助于设计在稀薄大气中收集这类大分子的中性气体浓缩器.     

Collisional depolarization of OH(A) studied by Zeeman quantum beat spectroscopy

The depolarization of the rotational angular momentum of electronically excited OH(2Σ) radicals through collisions with water molecules has been measured using Zeeman quantum beat spectroscopy. The new data have permitted the evaluation of OH(A) state-specific quenching and angular momentum depolarization cross-sections for superthermal OH(A) radicals with mean relative velocities centred around 3500 m s-1. The quenching cross-sections are compared both with values available in the literature, and with predictions based on a simple harpoon model, and are found to be in good qualitative accord with previous findings. For the lowest rotational levels studied, the depolarization cross-sections (which include contributions from both elastic and inelastic processes in OH(A)) are found to approach ～100 Å2, only slightly below the high-temperature cross-sections for rotational energy transfer determined elsewhere. The data suggest that under the present conditions rotational energy transfer is accompanied by significant depolarization. The cross-section for the translational moderation of superthermal OH(X) by water is also determined in the present study.     

碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布

采用准经典轨线方法研究了碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布,计算了产物分子CaBr的平均振动、转动和平动能量以及总可资用能量.结果表明,当碰撞能为7.54kJ/mol时,产物的能量主要为振动能量;随着碰撞能增加,产物的平动能和转动能增加,而振动能略微减小,最可几振动态向较低振动能级移动;反应物分子内能态分布对产物分子的内能态分布影响很小;反应基团越大,产物的振动能占总可资用能量的比例就越高.碰撞反应Ca+C2H5Br和Ca+nC3H7Br均存在两条竞争的反应路径迁移相碰和直接反应路径.前者产生高振动激发态产物CaBr,后者引起C-Br键断裂.当碰撞能增加时,两种反应均倾向于后者.     

Scattering of Li+ from LEED characterized W(110) and Si (111) surfaces at energies between 2 and 20 eV

Energy and angular distributions of Li⁺ ions scattered from W(110) and Si(111) surfaces have been measured for a wide range of scattering angles and for beam energies between 2 and 20 eV. The collision process can be explained in terms of binary collisions with single surface atoms, if the influence of the attractive part of the interaction potential is taken into account. A square well approximation for the potential makes it possible to predict the form of the energy spectrum as well as the behaviour of the angular distribution of the scattered particles for both systems. The influence of adsorbed atoms and molecules on the scattering behaviour has been investigated. Exposure of the W surface to H₂, O₂ and CO shows that surface coverages exceeding 10% of a monolayer very drastically influence the scattering. The results from the clean surfaces indicate that sufficiently precise measurements of the energy spectra of the scattered particles can yield very detailed information about the form of the interaction potential. The form of the energy spectra also contains information as to the extent of vibrational excitation of the surface atoms.