We experimentally investigate the vibrational state distribution of the cations after carbon monoxide(CO)molecules are irradiated by strong laser fields.Vibrational-resolved fluorescent spectrum is observed,which can be well assigned as the A^(2)Π(υ′=0-3)→X^(2)Σ+(υ″=0-3)transitions of the cations CO+,indicating the strong field ionization of the inner molecular orbital of CO.Relative distribution of vibrational states A^(2)Π(υ′=0-3)of CO+is retrieved from the measured spectrum and the Franck-Condon factors.It is found that the vibrational state distribution in strong field ionization of CO apparently deviates from the Franck-Condon-like distribution,but is in good agreement with the calculations,in which we include both the ionization rate and the overlapping between the vibrational wavefunctions of the neutral and cationic electronic states.The distribution of CO+(A^(2)Π,υ′)strongly depends on the laser intensity but is less dependent on the laser ellipticity.Analysis indicates the inter-nuclear distance-dependent ionization plays a significant role in the vibrational state distribution induced by strong field ionization of CO molecules.
Threshold photoelectron spectrum of CH_(2)F_(2)in the photon energy range of 12.45-14.10 eV was re-investigated by means of a combination of photo-electron-photoion coincidence experiments and density functional theory calculations.A series of vibrational peaks were distinctly observed in this range.Using optimized geometries and vibrational frequencies of the CH_(2)F_(2)neutral and its cation in ground state at the M06-2X/cc-pVTZ level of theory,Franck-Condon factor simulations were conducted.Taking into account anharmonicity influences,a perfect agreement between the simulated and experimental spectra has been achieved.From the reliable vibrational assignments,adiabatic and vertical ionization energies of CH_(2)F_(2)are derived as 12.371±0.010 eV and 13.281±0.010 eV,respectively.In addition,the experimental frequencies of four vibrational modes with ai symmetry for CH_(2)F_(2)+(X^(2)B_(1))ions are determined.
Xueqi CuiXinlang YangTongpo YuXiaoguo ZhouShilin Liu
颗粒物质生产、储存和输送等研究已经有悠久的历史,近些年来,虽然开展了关于颗粒物质的多方面的实验和模拟计算,但对其运动规律研究还很肤浅,描述颗粒物质的基本理论尚未建立。基于离散元法(discrete element method,DEM),用PFC软件生成了压强分别为0.1、1、10、100、1000、10000 Pa的不同维度的无摩擦颗粒体系,基于Hessian矩阵的简正模式分析法,编写了计算不同维度和压强下颗粒体系态密度的程序,进一步分析了维度和压强对颗粒体系态密度的影响。结果表明:一维颗粒体系的态密度不受压强影响。在低频下态密度几乎不随频率变化,在高频下态密度曲线随频率呈现振荡上升趋势。二维颗粒体系态密度曲线在某个特征频率之上出现一个平台,且该平台随着压强的增加而增加。低于某个特征频率下,三维颗粒态密度随频率呈幂率标度,随着压强增加曲线向高频移动。
The hydrogen abstraction reaction of methanol with fluorine atoms can produce HF and CH_(3)O or CH_(2)OH radicals,which are important in the environment,combustion,radiation,and interstellar chemistry.In this work,the dynamics of this typical reaction is investigated by the quasi-classical trajectory method based on a recently developed globally accurate full-dimensional potential energy surface.Particularly,the vibrational state distributions of the polyatomic products CH_(3)O and CH_(2)OH are determined by using the normal mode analysis method.It is found that CH_(3)O and CH_(2)OH are dominantly populated in the ground state when the reactants are at the ground ro-vibrational state.The OH stretching mode,torsional mode,H_(2)CO out-of-plane bending mode and their combination bands in the CH_(2)OH product can be effectively excited once the OH stretching mode of the reactant CH_(3)OH is excited to the first vibrationally excited state.Most of the available energy flows into the HF vibrational energy and the translational energy in both channels,while the radical products,CH_(3)O or CH_(2)OH,receive a small amount of energy,consistent with experiment,which is an indication of its spectator nature.
