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1.
本文利用高分辨的里德堡态氘原子标识-交叉分子束装置,研究了碰撞能为4.5~6.5 kcal/mol范围内Cl(~2P)[Cl(2~P_(3/2))和Cl~*(~2P_(1/2))]与D_2的反应.虽然自旋轨道激发态反应Cl~*(~2P_(1/2))+D_2在波恩-奥本海默(B-O)近似下本应是禁阻的,但实验中观测到了该反应的贡献.通过测量靠近后向的碰撞能相关的微分散射截面连线,发现低碰撞能下的产物主要来自于B-O近似禁阻的反应Cl~*+D_2.随着碰撞能的提高,自旋轨道基态反应Cl+D_2的反应性增加明显要比自旋轨道激发态反应Cl~*+D_2更快,并且在高碰撞能下成为产物的主要来源.实验结果表明:在低碰撞能下,Cl~*中自旋轨道激发态的额外能量,可以帮助B-O近似禁阻的反应Cl~*+D_2越过势垒;然而当碰撞能接近和高于反应势垒时,B-O近似允许的反应Cl+D_2占主导地位.Cl/Cl~*+D_2反应中B-O近似有效性的特征与共同位素反应Cl/Cl~*+H_2是一致的.  相似文献   

2.
本文使用交叉分子束方法研究了氟原子和振动激发态氘分子D2(v=1, j=0)的反应. 使用受激拉曼抽运的方法制备了振动激发的D2分子. 实验中未观测到来自于旋轨耦合激发态氟原子F*(2P1/2)与振动激发态D2分子的贡献. 观测到来自于旋轨耦合基态氟原子F(2P3/2)和振动激发态D2的反应信号,相应的产物DF分子布居于v''=2,3,4,5振动态上. 与振动基态反应F+D2(v=1,j=0)相比,振动激发态反应F+D2(v=1,j=0)生成的DF产物转动分布更“热”. 获得了振动激发反应的四个碰撞能在0.32至2.62 kcal/mol范围内的微分反应截面. 在最低的碰撞能0.32 kcal/mol下,所有振动态的DF产物都以后向散射为主. 随着碰撞能的增加,DF产物的角分布逐渐从后向转移到侧向. 测量了DF(v''=5)产物的前向微分散射截面随碰撞能变化的曲线. 前向散射的DF(v''=5)信号出现于1.0 kcal/mol. 在2.62 kcal/mol碰撞能下DF(v''=5)主要为前向散射.  相似文献   

3.
基于氢原子里德堡态飞行时间谱探测方法及多通道探测的优势,利用交叉分子束实验装置系统地研究了低碰撞能3.03∽17.97 meV内的F+HD→DF+H反应. 实验中清楚地观测到来自波恩-奥本海默近似禁阻的反应F*(2P1/2)+HD→DF+H和波恩-奥本海默近似允许的反应F(2P3/2)+HD→DF+H的贡献. 在后向散射方向上,波恩-奥本海默近似禁阻的反应F*(2P1/2))+HD的贡献远远大于波恩-奥本海默近似允许的反应F(2P3/2)+HD,表明非绝热效应在低碰撞能下F+HD→DF+H中扮演着重要角色. 并且,后向散射信号随着碰撞能的降低而单调降低,未出现反应共振的特征. 实验中还获得了低碰撞能3.03∽17.97 meV内波恩-奥本海默近似禁阻的和波恩-奥本海默近似允许的反应微分截面,其中最出乎意料的现象是:随着碰撞能的降低,产物的角分布由后向散射逐渐转变为侧向散射,这可能是在低碰撞下存在的某种未知反应机理引起的.  相似文献   

4.
一个化学反应的过程可能涉及多个绝热电子态,其中的非绝热耦合对反应机理起着重要的作用. 本文采用含时量子波包方法和轨线面跳跃方法研究了非绝热耦合对H+MgH+→Mg++H2反应的影响. 通过理论计算得到了绝热和非绝热近似下的反应态-态分辨的积分截面. 计算结果表明,当计算中忽略非绝热耦合时,反应遵循直接剥离的反应机理. 然而,当计算中包含非绝热耦合时,在反应过程中可以形成一个长寿命的激发态复合物(MgH2+)*,进而使反应遵循复合物形成反应机理. 通过轨线面跳跃计算,进一步揭示了直接剥离和复合物形成反应机理. 由非绝热耦合引起的复合物形成反应机理不仅提高了反应的活性,并且对产物的振动态分布具有显著影响.  相似文献   

5.
本文利用最近研制的低温离子阱-离子速度成像谱仪在冷离子束中研究了同位素质量分辨的79Br2+分子离子的[1+1]双光子激光解离动力学. 借助其14Σ-u,3/2态为中间态使79Br2+共振吸收两个光子至4∽5 eV区域的高激发态并发生解离. 利用离子速度成像技术获得了光解产物79Br+的二维速度分布和平动能释放谱. 通过平动能释放谱确定了不同解离能量处量子态分辨的解离产物通道分支比. 光碎片产物的角分布表明79Br2+分子离子的双光子解离是14Σ-u,3/2态的ΔΩ=0平行跃迁至一个Ω=3/2高解离态发生的. 由于分子激发态中的强自旋-轨道耦合作用,高激发的四重态很可能参与到实验观测的光解过程.  相似文献   

6.
当碰撞能很低,尤其是远低于反应势垒的时候,反应通常经过量子隧穿来进行. 目前,还没有明确的物理图像来描述反应物的转动激发对这类反应过程的影响. 本文基于里德堡态D原子飞行时间谱探测方法,利用多通道探测器交叉分子束装置研究了碰撞能44 cm-1∽164 cm-1下反应F+D2(v=0,j=0,1)→DF(v'')+D的动力学过程,并得到了振动态分辨的微分截面. 在可资用能相等时,通过调控反应的平动能,研究了D2转动激发对于反应的影响,发现反应物的转动比平动更有利于反应的进行. D2的转动激发导致产物DF的角分布和量子态分布发生显著变化. 本工作进一步加深转动激发对于反应的影响的理解,尤其是在反应能量远低于反应势垒的情况下.  相似文献   

7.
SELEX合作组发现的DsJ(2632)引起了很多的讨论, 同时也带来了激烈的争论. 它的自旋宇称还没有最后确定, 如果它真的存在, 它的夸克结构可能是奇特的. 以前有的文献假定DsJ(2632)是1的径向激发态, 我们假定它可能是夸克结构为qq,JP为2+的基态或者0+DsJ(2317)的第一径向激发态, 用Bethe-Salpeter方程重新计算了它的衰变宽度. 计算结果表明, 理论值和实验数据还是存在尖锐的矛盾.  相似文献   

8.
 对利用微波放电直接解离Cl2生成Cl, Cl与HN3反应生成NCl(a )和NCl(b1∑)的过程进行了实验研究。得到了较强的NCl(a 和NCl(b1∑)自发辐射光谱,考察了Cl2流量和He/Cl2配比对NCl(a 和NCl(b1∑)生成的影响。发现对于一定的He流量,Cl2流量对NCl(a 和NCl(b1∑)生成的影响存在一最佳范围,而最佳He/Cl2配比不是一定值,而是随He流量升高而变大,在实验所考察的He流量范围(5~40 L/min)内,最佳He/Cl 2配比在30∶1~100∶1之间。  相似文献   

9.
基于精确的势能面,研究D+OD+反应在0.0~1.0 eV碰撞能范围内的量子动力学. 用CS近似(centrifugal sudden approx-imation)的含时波包方法研究吸热的抽取反应通道(D+OD+→ O+D2+)和热中性的交换反应通道(D+OD+→D+OD+),计算两个通道的反应几率、总积分反应截面和热速率常数. 发现在交换反应的反应路径上存在一个凸起结构. 计算的总角动量J=0时的波包分布的含时演化清楚地表明凸状结构对两个通道的动力学有非常重要的影响.  相似文献   

10.
在193 nm的单色激光实验中,本文利用时间切片离子速度成像技术,研究了经193 nm双光子电离得到的Si2+的解离反应动力学过程. 根据实验得到的Si+离子的速度成像,观测到了两种离子直接解离通道:Si(3Pg)+Si+(2Pu)和Si(1D2)+Si+(2Pu). 电子基态的Si2分子处于v=0∽5的振动态上,其经过双光子电离后激发到Si2+离子的多个电子激发态势能面,生成主要通道Si(3Pg)+Si+(2Pu),其中v=1的解离信号最强. 此外,由于势能曲线22Πg与32Πg相同对称性引起的避免性势能面交叉,生成次要反应通道Si(1D2)+Si+(2Pu). 通道Si(1D2)+Si+(2Pu)的产物亦可以由生成的基态Si2+(X4Σg-)吸收一个193 nm光子后解离得到,其对应产物则具有更大的动能.  相似文献   

11.
使用三维含时波包方法在两个势能面上研究了Cl+H2(D2)反应.所使用的两个势能面都是从CW(Capecchi和Wener)势能面得到的,第一个是CW势能面的基态面加自旋轨道耦合修正,第二个是CW势能面的基态面没有自旋轨道耦合修正.在这两个势能面上得到了碰撞能从0.1到1.4 eV的积分截面以及反应几率.对于Cl与D2反应,考虑自旋轨道耦合后由于势垒高度的增加反应截面向高能处有一个平移,但Cl与H2反应在低能处的反应活性反而增大了,原因是虽然自旋轨道耦合效应增加了势垒高度,同时减小了势垒宽度,隧道效应更加明显,而隧道效应在低能处起着比较重要的作用,所以反应活性比较大.当碰撞能大于0.7 eV时,没有考虑自旋轨道耦合时势垒高度较低,因而反应活性较大.  相似文献   

12.
In our previous work we investigated electronically non-adiabatic effects in using crossed molecular beam scattering coupled with velocity mapped ion imaging. The prior experiments placed limits on the cross-section for electronically non-adiabatic spin-orbit excitation and electronically non-adiabatic spin-orbit quenching . In the present work, we investigate electronically non-adiabatic spin-orbit quenching for which is the required first step for the reaction of Cl* to produce ground state HCl+H products. In these experiments we collide Cl (2P) with H2 at a series of fixed collision energies using a crossed molecular beam machine with velocity mapped ion imaging detection. Through an analysis of our ion images, we determine the fraction of electronically adiabatic scattering in Cl* +H2, which allows us to place limits on the cross-section for electronically non-adiabatic scattering or quenching. We determine the following quenching cross-sections σ quench(2.1 kcal/mol) = 26 ± 21 ?2, σ quench(4.0 kcal/mol) = 21 ± 49 ?2, and σ quench(5.6 kcal/mol) = 14 ± 41 ?2.  相似文献   

13.
G2 ab initio molecular orbital calculations have been performed to study the potential energy surfaces (PESs) associated with the reactions of Cl+ in its 3P ground state and in its 1D first excited state with hydrogen sulphide. [H2, Cl, S]+ singlet and triplet state cations present very different bonding characteristics. The latter are systematically ion-dipole or hydrogen-bonded weakly bound species, while the former are covalent molecular ions. As a consequence, although the Cl+(3P) is 34.5 kcal mol?1 more stable than Cl+(1D), the global minimum of the singlet PES lies 37.3 kcal mol?1 below the global minimum of the triplet PES. Both singlet and triplet potential energy surfaces show significant differences with respect to those associated with Cl+ + H2O reactions as well as with SH2 reactions with F+. In both cases, the major product should be SH+ 2; SH+ and HCl+ being the minor products, in agreement with the experimental evidence. The estimated heat of formation for the most stable H2SCl+ singlet state species is 198 ± 1 kcal mol?1.  相似文献   

14.
The time-dependent quantum wave packet (TDWP) and quasiclassical trajectory calculations (QCT) are carried out for the Au(2S) + H2(X1+g) → AuH(X1+g) + H(2S) reaction on a global potential energy surface. The reaction probabilities at a series of J values, integral cross sections (ICSs) and differential cross sections of the title reaction are calculated by the TDWP method. For reaction probabilities, there are a mass of sharp oscillations at low collision energy, which can be attributed to resonances supported by the potential well. Due to the endothermicity of the title reaction, the total ICS shows a threshold about 1.53 eV. In order to further investigate the reactive mechanism, the lifetime of complex is calculated by QCT method. At the low collision energy, most intermediate complexes are long lived, which implies that the reaction is governed by indirect reactive mechanism. With the collision energy increasing, the direct reactive mechanism occupies the dominant position. Due to the change of the reactive mechanism, the angular distribution shifts toward the forward direction with collision energy increasing. The isotopic variant, Au + D2→AuD + D reaction, is also calculated by TDWP method. The calculated reaction probabilities and ICSs show that the isotope effect reduces the reactivity.  相似文献   

15.
A generalization of the Roach-Child semiempirical pseudopotential calculation for K + NaCl to several analogous dialkali halide systems has been used to elucidate the chemical interactions governing the reaction dynamics. The Li + LiF ground-state potential surface, which exhibits a ~ 20 kcal/mole basin for isosceles Li2F, is qualitatively similar to one obtained in a recent configurational interaction calculation. It is shown that regions of the Na2Cl ground-state surface corresponding to Na2 + interacting with Cl- can be described in terms of an ion-pair Rittner potential model similar to that employed for the alkali halides. Chemical trends in the triangular complex well depths satisfactorily account for the experimentally observed transition between the collision complex mechanism (Rb + KCl) and the osculating complex model (Li + KBr) for the alkali-alkali halide exchange reactions at thermal energies. For collinear configurations with the alkalis on opposite ends, avoided intersections between the lowest two potential surfaces are characterized in terms of diabatic surfaces computed from truncated basis sets. Crossings of these surfaces account for the vibrational-electronic energy transfer between alkali atoms and vibrationally excited alkali halides. The ionic X - + A 2 + potential surfaces are used to predict the product electronic excitation and partitioning of exoergicity in reactions of halogen atoms with alkali dimer molecules.  相似文献   

16.
The potential energy surfaces (PESs) for several electronic states involved in the reaction O+ (4S) + N2(X1Σ+) → NO+ (X1Σ +, v′) + N(4S) and the role of the ionic N2O+ intermediate have been investigated by ab initio calculations. The 4A″ PES, which correlates with the ground state educts, has a barrier of about 1 eV, and therefore at low collision energies the reaction cannot take place adiabatically on this surface. However, the spin-orbit coupling in the entrance channel allows the system to pass into the Renner-Teller system of the X2 Π electronic ground state of the N2O+ intermediate. The reaction then proceeds on these surfaces up to the region in the exit channel where a similar coupling allows it to reach the product quartet asymptote. At collision energies higher than about 1 eV, the reaction proceeds mainly on the adiabatic PES of the 4A″ state. The A2Σ+ state of N2O+ predissociates via a vibronic coupling with the B2Π state, and in bent structures via a spin-orbit coupling with the 4A″ component of the 4II state. The electronic structure of the B2Π state is found to be of crucial importance for the understanding of the reactive processes in low lying electronic states of N2O+.  相似文献   

17.
颜占先  周小清  戴薇 《中国物理》1997,6(4):275-282
In this paper, we have calculated and analyzed theoretically and consistently the absorption spectra, the ZFS and EPR parameters of the ground state, the Schottky low-temperature heat capacity, and the paramagnetic susceptibility of Ni(pz)4Cl2 (Dichlorotetrapyrazolenickel) complex by using d8[(1-C2)D*4h+C2D*2h] complete configuration mixing unified crystal field theory. The theoretical results agree with the experimental observation very well. We can give a complete and reasonable theoretical interpretation of the optical, thermal and magnetic properties of Ni(pz)4Cl2.  相似文献   

18.
方子韦  林成鲁  邹世昌 《物理学报》1988,37(9):1425-1431
本文研究了不同能量(5—600keV)和不同剂量(1014-1016atom/cm2)下的P2+和P+注入〈100〉单晶硅后的损伤及退火行为。实验结果表明,P2+注入所产生的损伤总是大于P+注入所产生的损伤。由移位效率之比ND*(mol)/2ND*(atom)所表征的分子效应随入射能量的改变而变化并在100keV(P2+),50keV(P+)处达到极大值。P2+与P+注入的样品,退火后的载流子分布也有某些区别。我们认为,产生这些分子效应的基本原因是位移尖峰效应,但当入射离子的能量较高时,还应该考虑离子、靶原子之间的多体碰撞效应的贡献。 关键词:  相似文献   

19.
Survey emission spectra in the region of 190–600 nm and time and service-life characteristics of a transverse nanosecond discharge in He/Ar/CF2Cl2(CCl4) mixtures at a pressure of 10–100 kPa are investigated. In the emission spectra, excited products of the decomposition of freons—C2(A−X), CN(B−X), Cl 2 * , C*, Cl*, and Cl+*— and the emission of ArF at λ=193 nm are revealed. The emissions of Cl 2 * at λ=258 nm and ArF at λ=193 nm were the most intense. The discharge in the He/Ar/CF2Cl2 mixture is a multiwave emission source with λ=258 nm Cl 2 * 193 nm ArF, and probably, 175 nm Arcl. It is of interest for applications in UV-VUV-range pulse photometry. The duration of the emission on Cl 2 * , ArF, ArI, ClI, and ClII transitions in the discharge in the Ar/CF2Cl2 mixture (P=10–20 kPa) was 200–300 nsec. With adding He and increasing pressure to 100 kPa the duration of the emission decreased by a factor of 1.5–2. The basic mechanisms of the formation of Cl2, ArF, and CN(B) molecules in the transverse-discharge plasma are considered. Uzhgorod State University, 46, Pidgirna Str., Uzhgorod, 294000, Ukraine. Translated from Zhurnal. Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 241–246, March–April, 1999.  相似文献   

20.
于坤  张晓美  刘玉芳 《物理学报》2013,62(6):63301-063301
基于相关一致极化4zeta(aug-cc-pVQZ)基组, 应用量子化学从头计算中高水平的多参考组态相互作用方法计算了BCl+ 两个离解极限B+(1Sg)+Cl(2Pu)和B (2Pu)+Cl+ (3Pg)的14个Λ-S态势能曲线. 在计算中考虑了Davidson修正(+Q)和标量相对论效应, 并首次在计算中考虑了BCl+ 的旋轨耦合效应, 获得了由能量最低的4个Λ-S态分裂出的7个Ω 态. 计算结果表明相同对称性的Ω 态的势能曲线存在着非常明显的避免交叉. 通过分析Λ-S态的电子结构, 得到了各态的电子跃迁特性, 并确认了电子态的多组态性质. 使用LEVEL程序通过求解径向的Schrödinger方程得到了束缚Λ-S 和Ω态的光谱参数De, Re, Te, ωe, ωeχe和Be. 通过和已有的Λ-S态X2+ 的实验数据进行对比发现, 本文所得的计算结果与实验结果非常一致. 而文中其他电子态的光谱参数均为首次报道. 关键词: 势能曲线 光谱参数 多参考组态相互作用方法 旋轨耦合  相似文献   

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