CF_3I在强红外场下的多光子解离

本文用TEA CO_2激光9.6R(14)支作激发光源,富里叶变换红外光谱仪作分析手段,NO,O_2作CF_3自由基的捕捉剂,研究了CF_3I红外多光子解离的动力学。实验发现,O_2和NO均可用来捕捉CF_3I的红外光解产物CF_3自由基。从对CF_3I的红外多光子解离率与外加气体压力的变化关系的研究,以及CF_3I红外多光子吸收的测量,揭示出该分子在受红外激光激发时,具有小分子的特性。同时也观察到外加气体对早期瓶颈效应的消除。在无碰撞及早期瓶颈效应可忽略状态下,用能量间隔主方程对多光子解离率与激光能量密度的变化关系作了拟合,得出了与实验比较一致的结果。     

CF2HCl分子在红外多光子解离时分子间的能量传递过程

The infrared multiphoton dissociation (IR MPD) of CF_2HCl by measuring the C_2F_4 product after laser irradiation is investigated, The dissociation fraction of CF_2HCl as a function of the CF_2HCl pressure, laser energy fluence and number of laser pulses is measured. Under the low pressure condition the bottleneck effect is observed. Under the collision condition the dissociation fraction of CF_2HCl is affected by the competition between rotaional hole filling (collisional repoputation of pumped rotational states) and collisional deactivation of excited CF_2HCl moleculae.     

杂环化合物的红外多光子解离机理的研究

采用TEA CO_2激光器研究了1,4-二氧六环、吡咯烷和噻吩等杂环化合物的红外多光子解离过程,探讨了解离机理,给出解离率与激光能流的关系。解离阈值分别为0.85、1.0、1.5J/cm~(-2)。     

CF_2HCl分子在红外多光子解离时分子间的能量传递过程

分子在强红外激光照射下可以吸收几十个红外光子而解离,目前人们已经对这一现象进行了广泛的研研。其中研究较多的分子有SF_6、CF_3I、CF_2HCl等。由于CF_2HCl分子在红外激光照射时解离过程比较简单,而且也是一个激光分离碳-13同位素有前途的工作介质,人们对CF_2HCl分子的红外多光子解离规律做了较深入的研究。Y.T.Lee等利用分子束的方法研研了CF_2HCl分子在红外多光子解离时的机制。J.C.Stephenson等以及R.D.Duperrex等测定了CF_2HCl分子在无碰撞条件下的瞬时解离规律,认为CF_2HCl分子具有明显的转     

飞秒强激光场下亚硝酰氯分子的电离和解离

Ionization and dissociation of nitrosyl chloride ClNO were studied using femtosecond laser mass spectra tech-nique.Strong fragmental ions NO~ and Cl~ were observed with the laser intensity varied from 3.2×10~(14) to 2.5×10~(15) W/cm~2.These fragmental ions were attributed to the direct dissociation of the parent ions.Electronic structurecalculations were also carried out with Hartree-Fock,density functional and correlated levels of theory to under-stand the possible fragmentation pathways.The very low N-Cl bond energy in the parent ion of nitrosyl chloride isa clear reason for the absence of ClNO~ and ClN~ ion peaks from the femtosecond laser mass spectrum.     

红外多光子解离亚磷酸三甲酯产生可见及紫外荧光的研究

近年来,科学家们为了寻找一种在可见区工作的化学激光体系,重新对一些高放热的磷化物的化学发光反应发生兴趣.对磷化物光解行为的研究表明,光解过程和产物与燃烧反应有许多相似之处.这是磷化物光解方面的初步探索.十年前,Merrow 和Nogar 曾用TEA CO_2激光对亚磷酸三乙酯P(OC_2H_5)_3进行了红外     

红外多光子离解——小分子碰撞多光子离解

目前,最有前途的激光分离同位素方法仍是多原子分子在强红外场作用下选择性无碰撞多光子离解。有关该方法的原理、装置、测试和动力学过程已有评述。现在利用这种方法分离同位素已进入工业规模研究。对于较大     

气态CF2ClBr的紫外光解离

本文研究了气态CF2ClBr在253.7nm紫外光照下的光解离过程及光氧化机理。CF2ClBr-O2体系光解离的主要产物CF2O, Cl2和Br2, 另外还有少量的CO2, SiF4生成; 该体系中CF2ClBr的解离为一级反应, 光解离速率常数为1.89×10^-^5s^-^1; CF2ClBr的表观量子产率近似为1。在这些基础上讨论了光解离过程及光氧化机理。     

呋喃分子多光子电离解离过程的反应通道

1引言呋喃分子在450nm附近的多光子电离实验中[1]，质谱中观察不到母体离子C4H4O＋，主要碎片离子的相对丰度C＋＞C2＋＝CHO＋＝C3H3＋．这些离子的选质量光谱研究表明它们是呋喃分子先吸收3＋1个光子电离为母体离子C4H4O＋，然后C4H4O＋再进一步吸收光子逐步解离产生．陕哺离子的初级解离过程已比较清楚[2－4]，吹响离子能量在1～5eV之间解离通道是：这三个平行解离反应可用RRKM理论来描述[4]．但是陕哺离子在高能量下的解离反应，特别是次级解离过程还不清楚，因此无法确定MPIF实验中观察到小离子碎片产生的机理，为此本文在速…     

CF自由基双光子共振增强多光子电离研究：3pRy dberg态的转动分析

利用Ar/CF4、Ar/CF2Cl2或Ar/CF3COOH混合气体的直流脉冲放电产生CF自由基,观测了260～360nm范围内转动分辨的CF自由基双光子共振增强多光子电离谱。分析表明,该段光 谱对应于CF自由基3pπD2Πr(ν'=2～6,r=3/2,1/2)←←X2Πr(ν"=0,r=3/2,1/2)的共振激发。对观测的振动带进行了转动分析,并获得了3p里德堡态的转动常数和自旋-轨道分裂值。     

CF3I分子ν4带高分辨激光光谱研究

CF_3I分子的转动常数很小, 其振动谱带的转动结构在一般分辨率的光谱中不能分辨。我们用分辨率达2×10~(-3) cm~(-1)的红外二极管激光光谱的方法观察到了ν_4带的近十个Q支, 和上千条~PP, ~RR线, 以及ν_4+ν_6←ν_6和ν4+ν_3←ν_3两个热带跃迁, 并归属了其中的一些谱线, 研究了ν_4带中可能存在的振转相互作用, 利用最小二乘法拟合, 得到了有关的分子常数。     

n-C3H7I和i-C3H7I的激光裂解

Studies on the photofragmentation of n-C_3H_7I and i-C_3H_7I have been carried out by a photofragment spectrometer with rotatable pulsed molecular beam crossed with KrF excimer laser beam. TOF spectra of the iodine atom fragments (Fig.1, 2) which show the separation of the primary photodissociation channels n-C_3H_7I→n-C_3H_7+I~*(~2P_(1/2)) n-C_3H_7+I(~2p_(3/2)) i-C_3H_7I→i-C_3H_7+I~*(~2P_(1/2)) i-C_3H_7+I(~2P_(3/2)) are obtatned at 12 different angles. The distribution of total translational energy E_(CM) of recoiling photofragments are then determined. The ratios I~*/I of the photodissociation channels of n-C_3H_7I and i-C_3H_7I are measured to be 1.61 and 0.96 respectively (Table 1). The ratios I~*/I obtained by photofragment translational energy measurement in this Lab~[3]. are good in agreement with most of results abtained by IR emission~[5] and LIF~[4] measurement except the data of i-C_3H_7I, which is much different from I~*/I=0.35 reported by Bershon~[4] using LIF method.The extent of internal alkyl fragment excitation E_(int)~R is also determined (Table 2) by energy balance. The fraction of the available energy (E_(av1)=E_(CM)+E_(int)~R) which goes into internal exciatation of the alkyl fragment increases from 12.5% for I~* channe of CH_3I to 64% for both channels of i-C_3H_7I. The results are consistent with direct impulsive dynamic model of unimolecular decomposition based on “soft” alkyl radicals.The facts that the ratio I~*/I decreases with increasing carbon atoms and that the difference of the internal excitation of alkyl radicals between the I~* (~2P_(1/2)) and I (~2P_(3/2)) channelsincreases with increasing carbon atoms should be related and important for better understanding the origin of the I(~2P_(3/2)) channel caused by the potential energy surface crossing~[3]. The results of the internal excitation of the alkyl radicals in the photodissociation are also valuable for prediction of secondary products during the UV photolysis of those alkyl iodides in the gas cell.     

CH3I分子束激光裂解产物的分布

The photofragmentation of CH_3I at 249 nm has been investigated by means of our crossed laser-molecular beam apparatus with rotatable supersonic beam source. The measured I~*/I yield ratio is about 4/1. The C—I bond dissociation energy obtained is 56±1 kcal mol~(-1). The vibrational energy distribution of CH_3 fragments has been roughly estimated.     

CF3Br的红外光化学和光物理

We present the optothermal and optoacoustic spectra of CF_3Br in TEA CO_2 laser 00°1—02°0 R branch. Three absorption peaks has been observed at R(14) line (1074.6 cm~(-1)), R(18) line (1077.3cm~(-1)), and R(22) line (1079.9cm~(-1)) respectively. The peak at R(22) coincides with the position of P branch of CF_3Br linear IR spectrum, but two peaks at R(14) and R(18) can be interpreted as the hot bands.We also studied the multiphoton dissociation of CF_3Br and carbon isotope seperation.     

CX3NO(X=F、Cl)分子结构和稳定性的ab initio研究

本文用STO-3G基组对分子CF_3NO(1)、CF_2ClNO(2)、CFCI_2NO(3)和CCl_3NO(4)的各种可能存在的稳定构型进行了研究. 结果表明:(1) 卤素与氧在同侧的构型比其它构型稳定; (2) 在同一分子中, Cl与O同侧比F与O同侧更为稳定; (3) 分子从1至4稳定性下降. 本文计算结果与实验符合较好。     

CF4在Al2O3基金属氧化物上的分解反应

考察了在无水条件下γ-Al2O3基金属氧化物M-Al2O3(M=Mg、La、Ba、Ce、Ni、P)与CF4反应转化为金属氟化物的反应. 结果表明, 在所筛选的金属氧化物中, γ-Al2O3的初活性较高, 但由于CF4分解时产生的强放热效应使未反应的γ-Al2O3发生了α相变, 致使CF4转化率急剧下降, 反应温度越高, γ-Al2O3的α相变越快, 活性下降就越快. CF4在MgO-Al2O3上分解时, Mg物种比Al优先氟化生成了MgF2, Mg物种的氟化反应及其产生的强放热效应使MgAl2O4结构发生了解体. 在Al2O3表面负载助剂P、Ni,提高了其热稳定性, 抑制了CF4高温分解时未反应的Al2O3发生α相变, 使更多的γ-Al2O3参与了CF4分解反应.     

碘乙烷激光裂解反应通道及产物的能量分布

用分子束和飞行时间技术测量了248 nm激光光解过程C_2H_5I→C_2H_5+I°(~2p_(1/2))和C_2H_5I→C_2H_5+I(~2p_(3/2))裂解碎片的平动能和内能分布。测得通道比I~*/I为2.37。根据实验结果, 对光解过程中电子激发态特性, 产生I(~2p_(3/2))通道的机理以及乙基自由基的振动激发作了讨论。     

VA族元素氢化物的紫外光解和多光子电离 Ⅳ. SbH3分子的紫外激光光解和多光子电离

用ArF激光(193 nm)光解锑化氢, 首次获得了在波长为403-700 nm间的SbH_2发射光谱, 其辐射寿命为70±20 ns。还检测到了五十余条Sb(6s→5p)在紫外区的光谱谱线以及离子信号。它们都是多光子过程的产物。     

VA族元素氢化物的紫外光解和多光子电离Ⅰ. NH3分子紫外激光光解

在光强为10~6 W cm~(-2)的ArF激光作用下, NH_3分子被光解为NH(A~(3Π))先后吸收两个193 nm光予, 经过NH_3(Ã ~1A_2″)和NH_2( Ã ~2A_1)两个中间物的过程。NH(A~(3Π)→X~(3∑~-))的发射光谱表明, 该产物具有7700 K的转动高温。此系NH_2在激发过程中剧烈的变角效应所致。我们利用高功率的紫外激光器及时间分辩的测量仪器, 系统地研究了这些分子的光谱能级, 反应、光解机理和电离过程等, 显然有重要的意义。