慢电子与亚稳态He（2^3S）弹性散射中极化势研究

本采用带有截断函数的极化势,为确定其中的可调参数,给出了一个经验公式：r↑-/r0=0.618。通过慢电子与亚稳态He(2^3S)弹性散射总截面的计算,表明本确定的极化势更准确地描述了慢电子与亚稳态He弹性散射的实际过程。     

Cl与C3D6H2和C3H6D2反应的立体动力学对比研究

在扩展的London-Eyring-Polanyi-Sato(LEPS)势能面上,利用准经典轨线法研究了碰撞能为Ecol=6.0 kcal/mol时Cl与C3D6H2和C3H6D2反应.在质心系中计算了极化微分反应截面(2π/σ)(dσ00/dtω)、两矢量相关的P(rθ)分布、三矢量相关的极角分布P(Φr)以及用θr和r表示的产物转动角动量的空间分布,计算结果与有关实验及理论结果符合得很好.通过对比研究Cl与C3D6H2、C3H6D2和C3H8在不同碳位上的反应,发现质量因子在此类反应中起着重要的作用.     

N2H4和He（2^3S）,Ne（^3P0,2）的解离激发反应

本文利用分子束和化学发光技术，在单次碰撞条件下，首次研究了Ｎ２Ｈ４与亚稳态原子Ｈｅ（２＾３Ｓ），Ｎｅ（＾３Ｐ０，２）的解离激发反应，探测到反应的激发态产物ＮＨ（Ａ＾３Π）的化学发光。Ｎ２Ｈ４与Ｈｅ（２＾３Ｓ）的解离激发反应还探测到ＮＨ（ｃ＾１Π）的化学发光。同样条件下，Ｎ２Ｈ４与Ａｒ（＾３Ｐ０，２）作用没有观察到ＮＨ（Ａ，ｃ）的发光光谱。利用计算机模拟化学发光光谱，求得激发态产物ＮＨ（Ａ＾３Π）和     

在N2中[VnCr3—n（μ3—O）（μ—O2CCH3）6（THF）3]X[n=0—3,X=Cl^—1,ClO4^—,（VO5）0.5^—]及[VnFe3—n（μ3—O）（μ—O2CCH3）6（THF）3]X（n=0—3,X=Cl^—1）

The reaction behavior of the title complexes have been investigated by means of in situ IR in nitrogen atmosphere. It has been found that they enabled the acetic acid to convert to acetone and methane in different temperatures. The results indicate that the sequence of the ketonization reaction activity for the clusters was [V3OAT] > [VFe2OAT], [V2CrOAT] > [Fe3OAT], [VCr2OAT] > [Cr3OAT] [OAT = (mu 3-O) (mu-O2CCH3)6 (THF)3], and the sequence of the methanation reaction activity for the clusters was [Cr3OAT] > [VCr2OAT], [V2CrOAT] > [V3OAT] > [VFe2OAT], [Fe2OAH]. The ketonization reaction activity of [Fe3OAT] were obviously lower than that of [Fe3OAH] [OAH = (mu 3-O) (mu-O2CCH3)6 (H2O)3] and the methanation reaction activity of [Cr3OAT] were also much lower than that of [Cr3OAH]. The difference between [Fe3OAH], [Cr3OAT] and [Fe3OAH], [Cr3OAH] mentioned above were discussed.     

Stereodynamics of the O（^3p） with H： （D2） （v = O,j =O） reaction

Quasi-classical trajectory theory is used to study the reaction of O（3p） with H2 （D2） based on the ground 3A″ potential energy surface （PES）. The reaction cross section of the reaction O＋H2→＋OH＋H is in excellent agreement with the previous result. Vector correlations, product rotational alignment parameters （P2（j′. k）） and several polarizeddependent differential cross sections are further calculated for the reaction. The product polarization distribution exhibits different characteristics that can be ascribed to different motion paths on the PES, arising from various collision energies or mass factors.     

He（2^3S）与N2O（X）Penning电离中的N2O^＋（A^2Σ^＋）生成速率及相…

在分子束条件下测量了Ｈｅ（２＾３Ｓ）＋Ｎ２Ｏ（Ｘ）→Ｎ２Ｏ＾＋（Ａ＾２Σ＾＋）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－反应的Ｐｅｎｎｉｎｇ电离光学光谱，求得了Ｎ２Ｏ＾＋（Ａ＾２Σ＾＋）态的初生态相对振动布居。以Ｈｅ（２＾３Ｓ）＋Ｎ２（Ｘ）→Ｎ＾＋２（Ｂ＾２Σ＾＋ｕ）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－为参考反应，测量了Ｈｅ（２＾３Ｓ）＋ＢＮ２Ｏ＾＋（Ａ＾２Σ＾＋）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－反应的速率常数ＫＮ２Ｏ＾＋（Ａ）     

Rotational and Vibrational State Distributions of CsH and Relative Reactivity in Reactions of Cs（6^2D,7^2D） with H2

By using a pump-probe technique, the nascent rotational and vibrational state distributions of CsH are obtained in the Cs（6^2 D,7^2 D） plus H2 reaction. The nascent CsH molecules are found to populate the lowest two vibrational （v″ = 0 and 1） levels of the ground electronic state. By comparing the spectral intensities of the CsH action spectra with those of pertinent Cs atomic fluorescence excitation spectra, the relative reactivity with 1-12 is in an order of6^2D3/2 〉 6^2D5/2 〉 7^2D3/2 〉 7^2D5/2. The rotational temperatures are found to be slightly below the cell temperature. The relative fractions （〈fV〉, 〈fR〉, 〈fT〉） of average energy disposal are derived as （0.2,0.12,0.68）, （0.2,0.12,0.68）, （0.07,0.04,0.89） and （0.07,0.04,0.89） for the 6^2D3/2, 6^2D5/2, 7^2D3/2 and 7^2D5/2, respectively. The major available energy is released as translation. These results support that the reaction mechanism of Cs（6^2 D,7^2 D） plus 112 is primarily a eollinear abstraction and not an insertion.     

氯代甲烷分子对电子激发态CH（A^2△,B^2Σ^—和C^2Σ^＋）的猝灭

本文用激光光解－荧光猝灭方法测定了ＣＨ３Ｃｌ对ＣＨ（Ａ，Ｂ和Ｃ）及ＣＨ２Ｃｌ２、ＣＨＣｌ３和ＣＣｌ４对ＣＨ（Ｃ）的猝灭速率常数。结果表明，氯代甲烷分子对ＣＨ（Ｃ）的猝灭速率常数近似于ＣＨ（Ｂ）的猝灭速率常数，而比ＣＨ（Ａ）的猝灭速率常数大，但都具有与气动速率相当的量线，表明化学反应在其中可能起着重要的作用，且ＣＨ（Ａ，Ｂ，Ｃ）的猝灭速率常数都随氯代甲烷分子中的Ｃ－Ｃｌ键数的增加而增大。我们用碰撞络     

利用原位红外光谱研究若干过渡金属氧化物-丙酸体系，Fe2Cr（μ3-O）（μ-O2CC2H5）6（H2O）3Cl*xH2O及Cr3（μ3-O）（μ-O2CC2H5）6（H2O）3NO3*xH2O的反应行为

利用原位红外光谱法研究标题化合作在N2 中的反应行为。发现它们在不同温度下能使丙酸分别转化为乙醛和戊酮。金属氧化物对丙酸的戊酮化反应活性顺序是 :Fe3O4 >MnO2 >Cr2 O3>Co2 O3>Ni2 O3,这顺序与下列簇合物对该反应的活性顺序类似 :[Fe2 MnOPH]>[Fe3OPH]>[Fe2 CrOPH]>[Fe2 CoOPH]>[Fe2 NiOPH]>[Cr3OPH][OPH =(μ3 O) (μ O2 CC2 H5) 6(H2 O) 3]。对于戊酮化反应 ,过渡金属氧化物的反应温度明显高于相应的 [Fe2 MOPH]的反应温度 ,这旁证了 [Fe2 MOPH]的活性组分不是其金属氧化物。还讨论了Fe3O4 ,Fe2 O3 对丙酸分别转化为乙醛和戊酮反应活性的明显差异。     

Quasi-classical Trajectory Study of Reaction O （^3P）＋HCl （v =2; j=1,6,9） →OH＋Cl

The reaction O（^3P）＋HCl （v=2; j= 1,6,9） → OH＋Cl is theoretically studied with a quasi-classical trajectory method （QCT） on the benchmark potential energy surface of the ground 3A＇＇ state [J. Chem. Phys. 119（2003）9550]. The QCT-calculated state-resolved rotational distributions are in good agreement with the experimental results. The rotational polarization of the product OH molecule becomes weaker as the initial HCl rotation is excited. The calculated results can be explained from the large mass factor cos2 β of the title reaction, the van der Waals well in the potential energy surface and the secondary encounters in the exit channel.     

配合物[Zn（DMF）2（H2O）4]·C8Cl4O4的合成及其结构的研究

采用溶剂挥发扩散法合成了配合物单晶[Zn（DMF）2（H2O）4]·C8Cl4O4,其中DMF为N,N′-二甲基甲酰胺。配合物为三斜晶系,P-1空间群,其晶胞参数为n=0．57680（10）nm．6=0．85991（14）nm,c=1．2030（2）nm,α=95．781（3）°,β=102．074（3）°,γ：98．594（2）°,V=0．57154nm^3,Z=1,Mr=585．51,Dc=1．701g／cm^3,F（000）=298,μ=1．594mm^-1,最终偏差因子R1=0．0315,ωR2=0．0914．和R1=0．0345,ωR2=0．0946,同时采用红外光谱分析、元素分析对其进行表征。