大气中HCO+和COH+异构体的动力学研究

使用经典轨迹法研究了离子型平行络合反应H+(1Sg)+C O(X1Σ+,V=0,1;J=0)→HCO+(X1Σ+)或COH+(X1Σ +)。该两反应均无阈能,络合物寿命较短,一般为7.0×10-12 sec左右,有效络合 反应能区较窄。当CO(X1Σ+)的V=0时,HCO+(X1Σ+)有相对较 宽的优势产物区,电负性和能量是决定优势产物的主要因素;当CO(X1Σ+)的V=1 时,COH+(X1Σ+)有相对较窄的优势产物区,角动量是主要因素。     

Si(3Pg)+CO(X1∑+)体系的平行络合竞争动力学

使用经典轨迹法研究了平行络合反应Si(3Pg)+CO(X1∑ +,V=0、1,J=0)→SiCO(X3∑-)或SiOC(X3∑-).该两个反应均无阈能,络合物寿命较长,一般在2.0×10-12sec左右,有效络合反应能区较窄(初始相对碰撞平动能Et≤37.6560 kJ.mol-1).当CO(X1∑+)的V=0或1时,较高稳定性的SiCO(X3∑-)在低能区(Et＜12.5520 kJ.mol-1)均具有相对明显的优势,空间位阻因素起决定作用;在中能区(12.5520≤Et≤37.6560 kJ.mol-1),空间位阻因素减弱,能量因素加强,两者的反应速率接近相等;在高能区(Et＞37.6560 kJ.mol-1),两个络合反应几乎不发生.     

碳化硅合成反应动力学研究

基于经典轨迹法研究了碳化硅合成反应C(3Pg) SiO(X1∑ ,V=0,1;J=0)→SiC(X1∑ ) O(3Pg)的动力学.该反应存在阈能,反应截面均存在一个极大值和最佳反应能量.当SiO(X1∑ )分别处于V=0、J=0和V=1、J=0状态时,反应阈能分别约为1.2552×103kJ.mol-1和1.1297×103kJ.mol-1,反应截面极大值分别为5.3742×10-3nm2和5.1824×10-3nm2,而最佳初始碰撞能Et(the Optimal InitialCollision Translation Energy)分别为3.3472×103kJ.mol-1和3.7656×103kJ.mol-1.在SiC的最佳产率区(即最佳反应能区),通过反应物的振动激发并不能使SiC产率明显提高,因此基态下SiC合成反应的最佳能区即为该反应的最佳产率区.     

铀与CO反应的分子动力学研究

基于CUO分子(X3A″)的多体展式分析势能函数, 用准经典的Monte-Carlo轨迹法研究了U+CO(0, 0)的分子反应动力学过程. 结果表明 在碰撞能低(<215 kJ/mol)时可以生成长寿命络合物CUO(X3A″), 并且该络合反应是无阈能反应; 碰撞能大于418.4 kJ/mol后, 先后出现置换产物UO和UC; 随着碰撞能进一步增大, CUO分子将被完全碰散成U, C和O原子, 而且反应U+CO(0, 0)→UO+C, U+CO(0, 0)→UC+O和 U+CO(0, 0)→U+O+C是有阈能反应.     

U+CO体系的分子反应动力学研究

基于CUO分子(X3A″)的多体展式分析势能函数,用准经典的MonteCarlo轨迹法研究了U+CO(0,0)的分子反应动力学过程.结果表明:在碰撞能低时(<215kJ.mol-1),可以生成长寿命络合物CUO(X3A″),并且该络合反应是无阈能反应,这一结论与前文用多体项展式理论计算的CUO分子势能曲线结果一致.碰撞能大于4184kJ.mol-1后,逐渐出现置换产物UO和UC,随碰撞能进一步增大,分子将被完全碰散成U,C,O原子,而且反应U+CO(0,0)→UO+C,U+CO(0,0)→UC+O和U+CO(0,0)→U+O+C是有阈能反应基于CUO分子(X3A″)的多体展式分析势能函数,用准经典的MonteCarlo轨迹法研究了U+CO(0,0)的分子反应动力学过程.结果表明:在碰撞能低时(<215kJ.mol-1),可以生成长寿命络合物CUO(X3A″),并且该络合反应是无阈能反应,这一结论与前文用多体项展式理论计算的CUO分子势能曲线结果一致.碰撞能大于4184kJ.mol-1后,逐渐出现置换产物UO和UC,随碰撞能进一步增大,分子将被完全碰散成U,C,O原子,而且反应U+CO(0,0)→UO+C,U+CO(0,0)→UC+O和U+CO(0,0)→U+O+C是有阈能反应 关键词： 玻色-爱因斯坦凝聚体 V型三能级原子 双模压缩态光场 光场正交压缩     

双自由基CH燃烧反应机理的研究

应用量子理论从头算和密度泛函理论(DFT)对双自由基CH(X2Π)与O2(X3∑g-)的反应机理进行了研究.在B3PW91/6-311G**水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,并计算了零点能和过渡态的虚频率.并由B3PW91/6-311G**给出了各物种的总能量.计算表明,反应物中自由基CH与O2反应主要在二重态势能面上进行,CH中的C原子可以插在O2分子中两个氧原子中间形成中间体1(2HCO2),中间体1(2HCO2)可以经过不同的反应通道形成不同的产物P1(1CO2 2H)和P2(1CO 2OH),各反应通道的反应热的计算与实验值吻合较好.     

原子—双原子的络合反应碰撞和振转非弹性碰撞——对H CC系统的应用

本文用准经典动力学原理与方法,研究了H(~2S)-CC(X~1Σ~ _8)的绝热碰撞。发现在碰撞能低时可以形成长寿命络合物HCC,且此络合反应碰撞是无能的。此外,还研究了振转非弹性过程H CC(V=J=0)→H CC(V′,j′)的一般规律,并指出传能过程T(V)→R是主要的。     

钒氢分子及离子的势能函数与垂直电离势

为了搞清储氢材料的机理,需了解VHn(n=0、 1、 2)分子及离子体系势能函数和稳定性的信息,本工作用原子分子反应静力学原理推导出了VHn(n=0、 1、 2)的基态电子状态及其离解极限.对H原子采用6-311 G**基组,对V原子采用SVP全电子基组,用B3PW91方法计算了它们的平衡几何、离解能,在此基础上分别计算了VH,VH 1的Murrell-Sorbie解析势能函数和基态VH 2的解析势能函数及其对应的力常数、光谱参数和垂直电离势.计算表明VH 离子的2Σ 和4Δ以及VH2 离子的1Σ 均具有对应于离子稳定平衡结构的极小点,说明它们可稳定存在.而VH (6Σ )、基态的VH2 (3Φ)和VH2 (5Σ )离子的离解能太小,应是不稳定的.     

HCCI燃烧过程化学发光光谱研究

在一台经改装单缸光学发动机机上,进行不同喷油策略和进气温度条件下均质压燃(HCCI)燃烧化学发光光谱实验研究。实验保证循环供油量一定,燃用正庚烷作为燃料,转速600 r.min-1,进气压力0.1MPa,控制2个不同的进气温度:95和125℃。化学发光光谱研究结果表明,低温反应阶段化学发光很弱,主要源于甲醛光谱;低温反应后期-负温度系数区-高温反应初始阶段主要发光来源还是甲醛光谱;高温反应阶段发光主要来源于CO—O*连续谱,同时在CO—O*连续谱上出现OH,HCO,CH,HCHO谱峰;高温反应后期化学发光明显减弱。与-30°ATDC喷油相比,-300°ATDC喷油时CO—O*连续谱发光强度更大,HCO和OH生成量更多,燃烧反应进行程度更深。较高进气温度下CO—O*连续谱发光强度更大,HCO和OH生成量更多。     

AlF的X1Σ+,A1Π和B1Σ+态的势能函数

使用SAC/SAC-CI和D95 、6-311 g及D95(d)等基组,分别对AlF的基态X1Σ 、第一简并激发态A1Π和第二激发态B1Σ 的平衡结构和谐振频率进行了优化计算.对所有计算结果进行比较,得出D95(d)基组为最优基组;运用D95(d)基组和SAC方法对基态X1Σ ,SAC-CI方法对激发态A1Π和B1Σ 进行单点能扫描计算,并用正规方程组拟合Murrell-Sorbie函数,得到了相应电子态的势能函数解析式,由得到的势能函数计算了与X1Σ 、A1Π和B1Σ 态相对应的光谱常数,结果与实验数据较为一致.     

Insights into the Maillard reaction. The mechanism of Schiff's base formation from the reaction force perspective

Schiff's base formation of the Maillard reaction is described from a theoretical viewpoint. The double proton transfer reaction was investigated within the frame of reaction force analysis in which global and local electronic properties were monitored within reaction regions defined along the reaction coordinate. Calculations based on density functional theory show that Schiff's base formation in the Maillard reaction occurs through an asynchronous double proton transfer, the second proton transfer being the determinant step of the reaction.     

Study of the structure of unstable nuclei through the reaction experiments

Along with the development of the radioactive nuclear beam facility, the study of the structure of unstable nuclei has progressed rapidly over the last few decades. Due to the weakly binding property, the structure information of the unstable nuclei comes primarily from the scattering or reaction experiments. Therefore it would be very important to understand clearly the reaction mechanism involved in the experiment. We outlined here the major reaction mechanisms which are adequate to the study of unstable ...     

On the various derivations of the energy dependence of the empirical optical potential

The predictions of the energy dependence of the real part of the empirical optical potential implied by the formulations based on nuclear reaction theories and on the multiple scattering approach are compared. The recent data on the nucleon-nucleon forward scattering amplitude obtained from phase-shift analyses, direct measurements and dispersion relations are used. The meaning of the local expression obtained in the multiple scattering formalism is discussed and it is shown that its implications agree with those derived by the nuclear-theories approach.     

Zeros of the scattering amplitude in the complex angle plane

The possibility of reconstructing the scattering amplitude with the aid of the zeros in the complex cos θ plane of the differential cross section is considered. The reconstruction process is demonstrated in two examples. The location of the zeros of the scattering amplitude is examined for the strong absorption and optical models. It appears that there exists a correlation between the position of the zeros and the strength of the absorption.     

A new measurement of the half-life of the Ge 0 state

With a Ge(Li) detector as the target, the half-life of the 0⁺ first excited state of ⁷²Ge has been remeasured. A value of 422±13 ns has been obtained.     

Lifetime of the 3.854 MeV state in 13C by the recoil-distance method

The lifetime of the 3.85 MeV state in ¹³C has been remeasured by the recoil-distance method using the ¹²C(d, p)¹³C reaction. The value of the mean life determined is τ = 13.0 ± 0.4 ps. This result is compared to previous measurements, both by the Doppler-shift attenuation method and the recoil-distance method.     

Correlations and the pion-nucleus optical potential

We investigate the influence of nucleon-nucleon correlations on the parameters of the pion-nucleus optical potential. In the (3, 3) resonance region the corrections can be as large as 30% and their nature is intermediate between well-known high- and low-energy limits. Binding and correlation effects add constructively below the resonance and destructively above.     

FC(O)O自由基与NO反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法,在6-311G(d,p)基组水平上研究了FC(O)O自由基与NO反应的微观机理,全参数优化了反应过程中各反应物、中间体、过渡态和产物的几何构型,在CCSD(T)水平上计算了它们的能量,振动分析结果证实了中间体和过渡态的真实性,从对FC(O)O与NO的反应机理的研究结果看,FC(O)O与NO反应为4条反应通道多步反应过程,其反应的主要通道是FC(O)O+NO→M3→TS6→M5→FNO+CO₂,其主要产物是自由基FNO和CO_{2关键词： 密度泛函理论 反应机理 反应通道}