Determination of the anion O-3 geometry by Franck-Condon simulations of its photoelectron spectrum

A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectroscopy of the anion O-3. Geometry optimization and harmonic vibrational frequency calculations have been performed on the (X～)1A1 state of O3 and (X～)2B1 state of O-3. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of O-3. The theoretical spectrum obtained by employing CCSD(T)/6-311+G(2d,p) values are in excellent agreement with the observed one. In addition, the equilibrium geometry parameters, re(OO)= 0.135 5±0.000 5 nm and θe(O-O-O) =114.5±0.5°, of the (X～)2B1 state of O-3, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.     

飞秒时间分辨质谱方法研究CF3I光电离动力学

利用飞秒双色泵浦 探测 (pump probe)飞行时间质谱方法研究了CF3 I分子多光子电离动力学 ,所用泵浦光及探测光的中心波长分别为 2 6 5和 398nm .获得了母分子离子CF3 I+ 信号及其碎片离子CF3 + 和I+ 信号的寿命衰减常数分别为 (96± 7)、(198± 13)和 (16 7± 6 )fs.这些离子产生的多光子通道机理不同 :CF3 I来自 (1+2′)跃迁 ,单光子泵浦光与CF3 IA带共振 ;驭光子泵浦光激发CF3 I分子到 5 pπ7sδ(2 Π1/ 2 )里德伯态 ,单光子探测光电离产生的母分子离子解离产生CF3 + ;I+ 来自 (2 +2′)和 (1+1′ +2′)激发过程     

IBr分子的多光子电离谱的分析

本文用多光子电离的方法,观察了IBr分子高电子态(E)的2光子共振跃迁,结合Franck-Condon原理,从IBr分子的振动谱分析,首次得到IBr(E)态的转动常数B’_(?)-(0.0653±0.0003)cm~(-1).     

NO分子A2Σ→X2Π双光子激光感生荧光光谱

以Nd∶YAG激光器抽运光学参变振荡器 /光学参变放大器做为激发源 ,得到了NO分子在 2 2 0～ 35 0nm波长范围内的双光子激光诱导荧光光谱 ,并将其归属于A2 Σ(ν′ =0 )→X2 Π(ν″ =1～ 8)跃迁 ,用最小二乘法拟合获得NO分子X2 Π态振动常量″ωe =(190 4 .7± 7.3)cm-1,″ωe ″xe =(14 .2± 1.2 )cm-1,″ωe″ye=- (0 .0 2 18± 0 .0 0 91)cm-1,及平衡位置的力常量k =(1.5 99± 0 .0 12 )× 10 3 N·m-1。计算了所得跃迁谱带的弗兰克康登因子及相对荧光强度 ,结果与实验观测值相符。这可为用激光诱导荧光光谱技术探测大气污染物NO分子提供理论及实验参考     

碰撞诱导振动能量转移：Cs2[B1∏u(v′=5)]+ N2→Cs2[B1∏u(v′=4，6)]+ N2

利用激光诱导荧光方法研究了Cs2[B1∏u(v′=5)]与N2的碰撞能量转移。脉冲激光激发Cs2基态至[B1∏u(v′=5)]态,池温保持在410K ,N2气压在1.5×102Pa至2.5×103Pa之间变化。荧光中含有直接荧光和碰撞转移荧光成分,记录直接荧光B1∏u(v′=5)→X1∑+g(v〞=0)的时间分辨强度。从荧光强度的对数值给出的直线斜率得到B1∏u(v′=5)→X1∑+g(v〞=0)的有效寿命,由Stern-Volmer方程,得到B1∏u(v′=5)→X1∑+g(v〞=0)的辐射寿命为（45±9）ns。B1∏u(v′=5)态与N2碰撞的猝灭总截面为（9.8±1.5）×10-15cm2。用类似的方法得到B1∏u(v′=4,6)能级的辐射寿命。在不同的N2气压下,测量B1∏u(v′=5,4,6)→X1∑+g(v〞=0)的时间积分荧光强度,首次得到v′=5→v′=4及v′=5→v′=6的碰撞转移截面分别为(3.9±0.8)×10-15cm2和(4.1±0.8)×10-15cm2。     

用能带理论研究GaAs(111)—(2×2)表面的原子结构

本文提出了一个由低能电子衍射能带理论计算所确定的GaAs(111)—(2×2)表面的空位模型。发现第一层间距d_1=0.203±0.005A(收缩75％±0.005A),第二原子层间距d_2=2.71±0.04A(膨胀11％±0.04A)和第三层间距d_3=0.78±0.02A(收缩4.4％±0.02A)。对此结构,在表面的As—Ga键长l_(AS_1)-Ga_1=2.449±0.001A,As的背键长l_(AS_1)-Ga_2=2.450±0.002A,其键角(α)为120.06°±0.04°,而悬挂键P的角(β)为93.56°±0.03°。     

硝酰自由基光电子能谱的理论研究

本文采用谐振子模型, 考虑Duschinsky效应，推得计算三维Franck-Condon因子的代数表示，且应用于研究硝酰自由基的光电子能谱的强度分布及振动结构。 对于HNO（ 3A″）– HNO‾（ 2A″）光脱附过程，通过Franck-Condon 因子计算，得到光电子能谱的谱线相对强度，理论上计算的光电子能谱与实验观测到的光电子能谱达到较好的一致；另外，在光谱模拟过程中，通过迭代Franck-Condon分析，拟合实验能谱得到阴离子HNO‾自由基 2A″电子态的几何结构：键长R(NO)是0.1335 ± 0.0005 nm，键角(HNO)是106.3 ± 0.5o 。     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下，测量了温度在283，298，308和318 K的反应速率常数，分别为(1.45±0.14)×10^-13，(1.18±0.11)×10^-13，(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程，获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内，未观察到该反应的速率常数存在压力相关.     

过程J/ψ→+X,X→Δ+π产生重子共振态X的研究

利用螺旋度角分布分析和推广的矩分析方法 ,讨论了J ψ衰变过程J ψ→p+X ,X→Δ +π ,其中p和Δ分别是反质子和自旋 -宇称为 (3 2 ) + 的Δ重子 ,给出了相应于自旋 -宇称为 (1 2 ) ± ,(3 2 ) ± 和 (5 2 ) ± 的重子共振态 (包括混杂重子态 )X的角分布和矩表达式 .它们可以用来确定重子共振态X的自旋     

金刚石(ⅠⅠⅠ)Ⅰ×Ⅰ表面的类石墨和类衬底结构

本文提出了一个由LEED能带理论计算所确定的金刚石(lll)1×1表面的类石墨一类衬底结构模型,发现最外的碳原子向内弛豫0.05±0.01A,第一双层空间距d_1=0.498±0.006A(收缩3.3％±0.006A),两个双层之间的空间距d_2=1.43±O.01A(收缩7.4％±0.01),第二双层空间距d_3=0.56±O.01A(膨脓8.7％±0.01A)。并用大π键理论说明了金刚石(lll)1×1表面的豫弛机理     

Electronic States of Difluorocarbene Calculated by Multireference Configuration Interaction Method

We investigate the geometries and energies of seven electronic states X~1A_1,A~1B_1,a~3B_1,B~1A_2,b~3A_2,C~1B_2and c~3B_2 of CF_2 carbene using internally contracted multireference configuration interaction methods including Davidson correction(icMRCI+Q) with different basis sets aug-cc-pVXZ(X=T,Q,5).For the first time,the potential energy curves of electronic states of CF2 related to the lowest dissociation limit are calculated at the icMRCI+Q/aug-cc-pVTZ level.The ab initio results will further increase our understanding of the structures and dynamics of electronic states of CF_2 radical.     

S3分子的几何结构: 分子轨道从头算和Franck-Condon分析

在考虑Dusehinsky效应情况下,给出了多维Franck-Condon因子的理论计算公式;利用分子轨道从头算,完成了S3分子的(～X)1A1态和S-3分子的(～X)2B1态的几何结构优化和谐振频率分析,模拟了S-3的光电子能谱.在光谱模拟中,利用迭代Franck-Condon分析,得到了S3分子的(～X)1A1态的几何构型参数:r(SS)=1.94±0.02 (°A)和∠((S-S-S)=117.35±0.05°.由所得的S3分子的键角对Nimols等人得的结果[J.Phys.Chem.1986.90:2574]给出一个新的解释.     

AsH(X~3∑~-)及AsH_2(X~2B_1)自由基的分子结构与解析势能函数

运用Gaussian 03程序包中的单双迭代三重激发耦合簇理论和相关一致五重基优化了AsH_2的基态结构,并在优化结构的基础上计算了它的离解能和振动频率.结果表明:AsH_2基态的平衡构型具有C_(2v)对称性,键长R_(As-H)=0,1508 nm,键角∠HAsH=91.2231°,离解能D_e(Has-H)=2.8795 eV,振动频率ν_1(α_1)=1013.3361 cm~(-1),ν_2(α_1)=2225.1347 cm~(-1),ν_3(α_1)=2233.7565 cm~(-1).这些结果与实验值较为相符.对H_2的基态使用优选出的cc-pV6Z基组、对AsH的基态使用优选出的cc-pV5Z基组进行平衡几何与谐振频率的计算并进行单点能扫描,且将扫描结果拟合成了Murrell-Sorbie函数.与实验数据及其他理论结果的比较表明,本文关于AsH(X~3∑~-)自由基光谱常数(D_0,D_e,R_e,ω_e,B_e,α_e和ω_eX_e)的计算结果达到了很高的精度并最为完整.采用多体项展式理论导出了AsH_2(C_(2v),X~2B_1)自由基的解析势能函数,其等值势能图准确再现了它的离解能和平衡结构特征.首次报导了AsH_2(C_(2v),X~2B_1)自由基对称伸缩振动等值势能图中存在的两个对称鞍点,对应于反应AsH+H→ABH_2,势垒高度约0.1512×4.184 kJ/mol.

Abstract：

The CCSD(T) theory in combination with the cc-pV5Z basis set is used to determine the equilibrium geometry, dissociation energy and vibrational frequencies of AsH_2 (C_(2v), X~2B_1) radical. By comparison, excellent agreement can be found between the present results and the experiments. The values obtained at present are of 0.1508 ran for the equilibrium bond length R_(As-H), 91.2231° for the bond angle ∠ HASH, 2. 8795 eV for the dissociation energy D_e (HAs-H) and 1013.3361 cm~(-1), 2225.1347 cm~(-1) and 2233.7565 cm~(-1) for the vibrational frequencies ν_1(α_1), ν_2(α_1) and ν_3(α_1), respectively. The equilibrium geometry,harmonic frequency and potential energy curve of the AsH(X~3∑~-) radical are calculated at the CCSD(T)/cc-pV5Z level of theory. The ab initio results are fitted to the Murrell-Sorbie function with the least-square method. The spectroscopic parameters are in excellent agreement with the experiments. The analytic potential energy function of the AsH_2 (C_(2v), X~2 B_1) radical is derived by using the many-body expansion theory. This function correctly describes the configuration and dissociation energy of the AsH_2 (C_(2v), X~2B_1) radical. Two symmetrical saddle points have been found at (0.160 nm,0.296 nm) and (0.296 nm,0.160 nm) ,respectively. And the barrier height is equal to 0.1512×4.184 kJ/mol.     

Theoretical study of potential energy curves,spectroscopic constants,and radiative lifetimes of low-lying states in an SeO molecule

<正>The low-lying potential energy curves of the SeO molecule are computed by means of an ab initio multireference configuration interaction technique,taking into account relativistic(scalar plus spin-orbit coupling) effects.The spectroscopic constants ofΩstates for X~3∑~-,a~1△,b~1∑~+,A~3Π,A′~3△,and A″~3∑~+ states are obtained,and they are in good accordance with available experimental values.The Franck-Condon factors and transition dipole moments to the ground state are computed,and the natural radiative lifetimes of low-lyingΩstates are theoretically obtained. Comparisons of the natural lifetimes ofΩstates with previous experimental results and those of isovalent TeO molecule are made.     

S2O‾自由基光电子能谱的Franck-Condon分析

本文考虑多振动模混合和热带效应,凭借谐振子模型,推得计算两维-四振动模Franck-Condon重叠积分的解析表示,且应用于S2O‾ 自由基光电子能谱的理论研究。对于S2O( 1A′) – S2O‾( 2A″) 光脱附过程,结合分子轨道从头算和密度泛函理论,计算Franck-Condon因子,从而得到电子跃迁振动谱线的相对强度,理论上得到的光电子能谱与实验上观测到的能谱达到较好的一致;进一步在光谱模拟过程中,拟合实验能谱得到可靠的负离子自由基S2O‾电子态（ 2A″）的几何结构参数：键长R(SS) = 2.008 +/-0.005Å 和 R(SO) = 1.519+/-0.005Å.     

The X2 Pi and A2 sigma states of FCN+ and ClCN+ : ab initio calculations and simulation of the HeI photoelectron spectra of FCN and ClCN

Geometry optimization and harmonic vibrational frequency calculations at the CASSCF, MP2 and CCSD(T) levels with basis sets up to 6-311G(2df) quality were carried out on the X¹Σ⁺states of FCN and ClCN and the X²Π and A²Σ⁺ states of their cations. Adiabatic ionization energies were calculated up to the CCSD(T)/6-311G(3df)//CCSD(T)/6-311G(2d) level. Some B3LYP calculations were performed also for the ground states of the neutral molecules and the cations. Franck-Condon simulations were performed for the first two bands in the He I photoelectron spectra of FCN and ClCN by employing the ab initio computed geometries and frequencies. By comparing the observed and the simulated spectra obtained from different CN and CX (X = F or Cl) ionic bond lengths chosen on the basis of the ab initio computed values, the following structural parameters are obtained for the two lowest-lying states of FCN⁺ and ClCN⁺ (the method of deriving the uncertainties is described):     

Determination of the excited state structure of 7-azaindole using a Franck-Condon analysis

The change in structure of 7-azaindole upon electronic excitation was determined by a Franck-Condon analysis of the intensities in the fluorescence emission spectra obtained via excitation of six different vibronic bands. A total of 107 emission band intensities were fit, together with the changes in the rotational constants of four 7-azaindole isotopomers. The geometry change of the ring framework upon electronic excitation from the electronic ground state to the ¹L_b state (ππ*) can be described by an overall expansion of the pyridine ring of 7-azaindole, with minor changes of the pyrrole ring. The resulting geometry changes are interpreted on the basis of ab initio calculations.     

A theoretical study of the 21Ag ← 11Ag two-photon transition and its vibronic band in trans-stilbene

The two-photon spectrum of the 2¹A_g ← 1¹A_g transition in trans-stilbene has been calculated at the complete active space self-consistent field (CASSCF) level of theory. Energies were obtained at the complete active space second-order perturbation (CASPT2) level of theory, while the geometries of both the initial and final states were optimized at the CASSCF level. The energy and the geometry optimizations were performed using an active space of 14 electrons in 14 active π orbitals. The vibrational frequencies of both states and the two-photon transition (TPT) cross-section were calculated with a smaller active space where the two lowest π orbitals were kept inactive. A newly implemented algorithm, in the quantum chemical package Molcas was used to determine the two-photon transition intensity. This method requires only the linear response of the CASSCF wavefunction. Furthermore, the vibronic structure of this TPT was studied. The Franck-Condon factors were obtained by calculating the overlap between the vibrational states involved, which were determined from the force fields of both the initial and final states, at the CASSCF level of theory. The results are in agreement with experiment.     

碳原子线的电子传输特性

单分子电子器件的电子传输特性是当前分子电子学领域研究的热点.本文采用第一原理的ab inito法与格林函数方法,对Au电极-碳原子线-Au电极体系的电子结构以及电子传输等特性进行了分析,给出了C5、C10与C15原子线的电导 -电压曲线与伏安曲线.研究结果表明:碳原子线与Au电极之间的"接触"(结合)既有共价键的成分,又有离子键的成分;碳原子线的电导率及伏安特性具有特殊的量子效应和尺寸效应.