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1.
刘冬梅  张树东 《物理学报》2012,61(3):33101-033101
运用含Davidson修正的多参考组态相互作用方法,在aug-cc-pVTZ基组水平上,对BeCl分子基态和相同多重度的几个低电子激发态进行了势能扫描计算.通过群论原理确定各电子态对称性及离解极限.将其中基态(X2Σ+)和第一激发态(A2Π})对应的势能曲线拟合到Murrell-Sorbie解析势能函数形式,得到基态(X2Σ+)的离解能及主要光谱常数(括号中为文献[6]提供的实验值)为De=3.74eV,Re=0.18173nm(0.17970),we=857.4cm1(847.2),wexe=5.03cm-1(5.14),Be=0.7103cm-1(0.7285),αe=0.0059cm-1(0.0069),第一激发态(A2Π)的De=3.02eV,Re=0.18369nm(0.18211),we=832.7cm-1(822.1),wexe=5.93cm-1(5.24),Be=0.6953cm-1(0.7094),αe=0.0065cm-1(0.0068),计算结果与实验值符合得较好.另外,通过Level程序求解双原子径向核运动的Schrödinger方程得到J=0时BeCl分子这两个电子态的全部振动能级.  相似文献   

2.
王杰敏  张蕾  施德恒  朱遵略  孙金锋 《物理学报》2012,61(15):153105-153105
采用包含Davidson修正多参考组态相互作用(MRCI)方法结合价态范围内的最大相关一致基As/aug-cc-pV5Z和O/aug-cc-pV6Z, 计算了AsO+ (X2+)和AsO+(A2∏)的势能曲线. 利用AsO+离子的势能曲线在同位素质量修正的基础上, 拟合出了同位素离子75As16O+75As18O+的两个电子态光谱常数. 对于X2+态的主要同位素离子75As16O+, 其光谱常数Re, ωe, ωexe, Be和αe分别为 0.15770 nm, 1091.07 cm-1, 5.02017 cm-1, 0.514826 cm-1和0.003123 cm-1; 对于A2∏态的主要同位素离子75As16O+, 其Te, Re, ωe, ωexe, Be和αe分别为5.248 eV, 0.16982 nm, 776.848 cm-1, 6.71941 cm-1, 0.443385 cm-1和0.003948 cm-1. 这些数据与已有的实验结果均符合很好. 通过求解核运动的径向薛定谔方程, 找到了J=0时AsO+(X2+)和AsO+(A2∏)的前20个振动态. 对于每一振动态, 还分别计算了它的振动能级、转动惯量及离心畸变常数, 并进行了同位素质量修正, 得到各同位素离子的分子常数. 这些结果与已有的实验值非常一致. 本文对于同位素离子75As16O+(X1+), 75As18O+(X1+), 75As16O+(A1∏)和75As16O+(A1∏)的光谱常数和分子常数属首次报导.  相似文献   

3.
制备出确定旋轨态的OCS+(X2∏)离子,在260~325 nm波长范围内研究了OCS+经由B2+←X23/2(000)和B2+←X21/2(000,001)跃迁的分质量光解离谱.由光解离谱得到OCS+(B2+)电子态的光谱常数υ1(CS stretch)=828.9(810.4) cm-1,υ2(bend)=491.3 cm-1和υ3(CO stretch)=1887.2 cm-1.在B2+←X2∏跃迁谱中只能观察到B2+(010)←X21/2(000)跃迁的谱峰, 而观察不到B2+←X23/2(000)跃迁的谱峰. 用X2∏电子态的(000)21/2和(010)2+1/2电子振动能级之间的K耦合解释了这种B2+的υ2弯曲振动模的激发对X2∏电子态的旋轨分裂分量(Ω=1/2,3/2)的相关性  相似文献   

4.
基于之前的激光诱导荧光激发谱工作,采用激光诱导荧光色散谱技术直接侦测中性FeS基电子态X5¢振动能级到v″=3而获得其振动常数. 所得FeS(X5△)振动频率值(518±5 cm-1)和最近的光电子能谱测量值(520±30 cm-1) [J. Phys. Chem. A 107, 2821 (2003)]符合得较好,该光电子能谱测量值是之前唯一报道的FeS电子态振动频率的实验值. 通过比较实验结果和相关文献(主要来自理论预测),确定FeS的基态是X5△态.  相似文献   

5.
闵志元  李重德  王嘉珉  龚顺生 《物理学报》1992,41(12):1943-1949
使用脉冲光学双共振方法研究了碘分子“E”带离子对态,激发光总能量范围为43180—43600cm-1。实验获得了“E”带两个尚未见报道的离子对态E1(13≤V′(E1)≤17)和E2(15≤V′(E2)≤19),其中T(e1)=41909.13±1.786cm-1,T(e相似文献   

6.
BES合作组 《中国物理 C》1998,22(11):961-968
分析北京谱仪(BES)收集的4.03GeV质心系能量下e+e对撞数据,选出e+e→τ±τ+→e±X+v′S事例,X±可以为μ±±±,拟合τ→ev′s中电子的能谱,得到τ→ev′s中Michel参数为ρτ→e=0.705,此结果与标准模型的预言相符合.  相似文献   

7.
韩晓琴  肖夏杰  刘玉芳 《物理学报》2012,61(16):163101-163101
采用Gassian09程序包中的多种方法对OH, OCI, HOCI分子的基态结构进行优化计算, 优选出QCISD/6-311G(2df), B3P86/6-311+G(2df)方法分别对OH(X2), OCI(X2)分子进行计算, 得到平衡核间距ROH=0.09696 nm, ROCI=0.1569 nm, 谐振频率ω(OH)=3745.37 cm-1, ω(OCI)=892.046 cm-1, 与实验结果非常符合. 用Murrell-Sorbie势能函数对OH和OCI分子的扫描势能点进行拟合, 其扫描点都与四参数Murrell-Sorbie函数拟合曲线符合得很好.优选出QCISD(T)/D95(df, pd)方法对HOCI分子进行计算, 得到基态为X1A', 键长ROH =0.0966 nm, 键角∠HOCI=102.3°, 谐振频率ω1(a1)=738.69 cm-1, ω2(b2)=1260.25 cm-1, 离解能De=2.24eV. 通过比较发现这些结果与实验值符合得很好,并优于文献报道的结果. 随后计算出了力常数, 在此基础上,推导出HOCI分子的多体展式势能函数.报道了HOCI分子对称伸缩振动势能图中在H+OCI →HOCI反应通道上有一鞍点, H原子需要越过1.74eV的能垒才能生成HOCI的稳定结构, 在Cl+OH→HOCI通道上不存在明显势垒, 容易形成稳定的HOCI分子.  相似文献   

8.
施德恒  牛相宏  孙金锋  朱遵略 《物理学报》2012,61(9):93105-093105
采用内收缩多参考组态相互作用方法和相关一致基aug-cc-pV6Z, 对BF自由基X1+和a3∏ 态的势能曲线进行了研究. 计算是在0.095---1.33 nm的核间距内进行的. 为获得更准确的结果, 计算中还考虑了Davidson修正、相对论修正及核价相关修正对势能曲线的影响. 相对论修正采用的方法是二阶DouglasKroll哈密顿近似, 修正计算是在cc-pV5Z基组水平上进行的. 核价相关修正使用的是cc-pCV5Z基组. 利用得到的势能曲线, 拟合出了各种修正下BF自由基X1+和a3∏ 态的光谱常数De, Re, ωe, ωexe, ωeye, Be和αe、并与实验结果进行了比较. 结果表明: 考虑Davidson修正、相对论修正和核价相关修正后得到的光谱常数最接近实验结果. 利用修正后的势能曲线, 通过求解径向振转Schrödinger方程, 找到了转动量子数J = 0时这两个电子态的全部振动态, 并计算了每一电子态前20个振动态的振动能级、惯性转动常数和离心畸变常数, 其值与已有的实验结果较为一致. 本文得到的光谱常数和分子常数达到了很高的精度, 能为进一步的光谱实验提供可靠的参考.  相似文献   

9.
使用密度泛函理论B3LYP和B3P86,以及组态相互作用方法CCSD(T)和QCISD, 利用多个基组对7Li2(X1Σ+g)分子的平衡核间距(Re)、谐振频率(ωe)和离解能(De)进行了计算, 发现在CCSD(T)/cc-PVQZ理论水平下得到的结果(Re相似文献   

10.
段一士  朱重远 《物理学报》1965,21(1):103-113
本文通过强作用K-π中间态,利用色散关系理论计算了Г(Kμ3+)/Г(Kα3+),Г(K20→πμ+ν)/Г(K20→πe+ν),{Г(K20→πe+ν)+Г(K20→πe-ν)}/Г(Kα3+)分支比及Kμ3+衰变中的μ谱,当选择定则|ΔI|=1/2及ΔS=+ΔQ被破坏,并且Iz=1/2及Iz=3/2的振幅f3/2 1/2(0)及f3/2 3/2(0)不等时,上述分支比与实验能很好符合。在本文的理论中,形式因子不是常数。  相似文献   

11.
The structural stability and electrical resistivity of nanocrystalline Cr–N and V–N coatings prepared by ion beam-assisted deposition were studied. The results showed that under helium ion irradiation up to doses of 1.0.1017 ion/cm2 the fine-crystalline objects successively increase their resistance without apparent structural changes. The subsequent dose increase leads to gas-vacancy void formation and chromium nitride structure destruction. The presence of the initial closed porosity in vanadium nitride favors its structural stability at investigated maximum damage doses.  相似文献   

12.
Ultrathin films of vanadium nitride (1-20 monolayers = nanolayers) with (1 1 1) orientation have been grown on a Pt(1 1 1) surface by reactive evaporation of vanadium in NH3 atmosphere. The VN(1 1 1) surfaces have been investigated by X-ray and UV photoelectron spectroscopy, LEED, work function measurements, and ab initio DFT calculations. Nearly stoichiometric, well-ordered VN0.9 overlayers with their (1 × 1) unit cells rotationally aligned to the high symmetry directions of the Pt substrate have been obtained after annealing the films deposited at 300-500 °C in vacuum. The experimental valence band spectra have been compared to the theoretical density of states for differently terminated VN(1 1 1) surfaces, i.e. V and N terminated surfaces, bare and with chemisorbed hydrogen. The comparison suggests that the VN(1 1 1) nanolayers are terminated by a hexagonal layer of vanadium atoms, possibly covered with some chemisorbed hydrogen (which may originate from the preparation procedure). The VN nanolayer growth on Pt(1 1 1) follows a Stranski-Krastanov layer-plus-island growth mode.  相似文献   

13.
利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C5H7+,C5H5+,C4H5+,C3H6+,C3H5+,C3H4+,C3H3+的C2H3+的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.  相似文献   

14.
杨立书  盛六四 《光学学报》1995,15(10):359-1361
用合肥国家同步辐射实验室光化学站的实验装置研究了苯分子的光电离质谱,从所得光电离效率谱精确地定出了苯分子的电离势及苯离子的出现热,并首次报道了三个苯离子的离解能。  相似文献   

15.
甲胺分子的同步辐射光电离解离质谱   总被引:4,自引:0,他引:4       下载免费PDF全文
在超声射流冷却条件下,利用同步辐射光源,结合飞行时间质谱对CH3NH2分子在60—140nm波长范围内的光电离解离进行了研究.主要动力学过程为母体离子的解离过程.CH2NH2+和CH3+由CH3NH2+在高能量时解离生成,而CH2NH2+的1,1脱H2过程则产生其他离子.CH3NH2分子的电离势(IP)为916±001eV,和分子轨道能量计算的理论值符合得非常好,并获得CH3NH2+和CH2NH2+的生成热分别为860±05kJmol和7541kJmol. 关键词: 同步辐射光电离 飞行时间质谱 电离势 生成热  相似文献   

16.
We present the first experimental results of a technique called photoionization microscopy. Photoelectrons ejected in threshold photoionization of Xe are detected in a velocity map imaging apparatus, and interferences between various trajectories by which the electron moves from the atom to the detector are observed. The structure of the interference pattern, which contains the transverse component of the electronic wave function, evolves smoothly with the excess energy above the saddle point. The main observed features are interpreted within the framework of the semiclassical approximation.  相似文献   

17.
Binding energies of a charged exciton as a function of well width of a GaAs/GaAlAs corrugated quantum well are investigated. The calculations have been performed by the variational method based on a two parametric trial wave function within a single band effective mass approximation. We have also included the effect of nonparabolicity of the conduction band of GaAs. We study the spectral dependence of the charged exciton in a GaAs/GaAlAs corrugated quantum well as a function of well width. The photoionization cross section for the charged exciton placed at the center of the quantum well is computed as a function of normalized photon energy. The cross-section behavior as a function of incident energy is entirely different in the two cases of radiation being x-direction (along the growth direction) or z-direction. The interband emission energy as a function of well width is calculated and the dependence of the photoionization cross section on photon energy is carried out for the charged excitons. The resulting spectra are brought out for light polarized along and perpendicular to the growth direction. The results show that the charged exciton binding energy, interband emission energy and the photoionization cross section depend strongly on the well width. Our results are compared with the other existing literature available.  相似文献   

18.
The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods.The geometries and frequencies of the reactants,transition states and products have been performed at B3LYP/6-311++G (d,p) level,and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level.The ionization energies of toluene and the appearance energies for major fragment ions,C7H7+,C6H5+,C5H6+,C5H5+,are determined to be 8.90,11.15 or 11.03,12.72,13.69,16.28 eV,respectively,which are all in good agreement with published experimental data.With the help of available published experimental data and theoretical results,four dissociative photoionization channels have been proposed:C7H7++H,C6H5++CH3,C5H6++C2H2,C5H5++C2H2+H.Transition structures and intermediates for those isomerization processes are determined in this work.Especially,the structures of C5H6+ and C5H5+ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.  相似文献   

19.
The photoionization and photodissociation of 1,4-dioxane have been investigated with a reflectron time-of-flight photoionization mass spectrometry and a tunable vacuum ultraviolet synchrotron radiation in the energy region of 8.0-15.5 eV. Parent ion and fragment ions at m/z 88, 87, 58, 57, 45, 44, 43, 41, 31, 30, 29, 28 and 15 are detected under supersonic conditions. The ionization energy of DX as well as the appearance energies of its fragment ions C4H7O2+, C3H6O+, C3H5O+, C2H5O+, C2H4O+, C2H3O+, C3H5+, CH3O+, C2H6+, C2H5+/CHO+, C2H4+ and CH3+ was determined from their photoionization efficiency curves. The optimized structures for the neutrals, cations, transition states and intermediates related to photodissociation of DX are characterized at the B3LYP/6-31+G(d,p) level and their energies are obtained by G3B3 method. Possible dissociative channels of the DX are proposed based on comparison of experimental AE values and theoretical predicted ones. Intramolecular hydrogen migrations are found to be the dominant processes in most of the fragmentation pathways of 1,4-dioxane.  相似文献   

20.
Vanadium nitride (V-N) thin films were grown using a reactive d.c. magnetron sputtering process, from a vanadium target (99.999%) in an Ar/N2 gas mixture at different deposition bias voltage. Films were deposited onto silicon (1 0 0) and RUS-3 steel substrates at 400 °C. Structural, compositional, mechanical and electrochemical characterizations were performed by X-ray diffraction (XRD), elastic forward analysis (EFA), nanoindentation, electrochemical impedance spectroscopy (EIS), and Tafel polarization curves, respectively. X-ray diffraction patterns show the presence of (1 1 1) and (2 0 0) crystallographic orientations associated to the V-N cubic phase. Nanoindentation measurements revealed that when the bias voltage increases from 0 V to −150 V the hardness and elastic modulus are increased from 11 GPa to 20 GPa and from 187 GPa to 221 GPa, respectively. EIS and Tafel curves showed that the corrosion rate of steel, coated with V-N single layer films deposited without bias voltage, diminishes 90% compared to the steel without this coating. On the other hand, when the V-N coating was deposited at the highest d.c. bias voltage (−150 V), the corrosion rate was greater than in the steel coated with zero-voltage (0 V) V-N films. This last result could be attributed to the formation of porosities produced by the ion bombardment during the deposition process.  相似文献   

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