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 共查询到19条相似文献,搜索用时 250 毫秒
1.
陈恒杰 《物理学报》2013,62(8):83301-083301
利用单双激发多参考组态相互作用方法获得了LiAl分子基态X1+及七个激发态a3, A1, b3+, c3+, B1, C1+, d3的势能曲线, 通过势能曲线得到各态的平衡核间距Re, 进而求得绝热激发能和垂直激发能.计算结果表明:c3+ 电子态是一个不稳定的排斥态, A1态是一个较弱的束缚态, 其余6个电子态均为束缚态; b3+c3+态之间存在预解离现象; 8个电子态分别解离到两个通道, 即Li(2S)+Al(2P0)与Li(2P0)+Al(2P0). 接着将势能曲线拟合到Murrel-Sorbie解析势能函数形式, 据此获得各态的光谱数据:基态X1+的平衡键长为0.2863 nm, 谐振频率为316 cm-1, 解离能De为1.03 eV, 激发态a3, A1, b3+, c3+, B1, C1+, d3的垂直激发能依次为0.27, 0.83, 1.18, 1.14, 1.62, 1.81, 2.00 eV; 解离能依次为1.03, 0.82, 0.26, 排斥态, 1.54, 1.10, 0.93 eV, 相应谐振频率 ωe为339, 237, 394, 排斥态, 429, 192, 178 cm-1. 通过求解核运动的薛定谔方程找到了J=0时 LiAl分子7个束缚电子态的振动能级和转动惯量. 关键词: LiAl 光谱常数 势能曲线 振动能级  相似文献   

2.
王庆美  任廷琦  朱吉亮 《物理学报》2009,58(8):5270-5273
采用量子力学从头计算方法,运用单双取代二次组态相互作用和单双(三)取代二次组态相互作用并考虑基组6-311++G(3df,3pd)计算优化了GaH(D,T)分子基态X1Σ+的结构和离解能.并采用最小二乘法拟合改进的Murrell-Sorbie函数得到了相应的势能函数.计算得到的光谱常数与实验光谱数据符合得很好. 关键词: GaH(D T)分子基态 势能函数 Murrell-Sorbie函数  相似文献   

3.
黄多辉  王藩侯 《物理学报》2009,58(9):6091-6095
以aug-cc-pVQZ,cc-pV5Z,6-311++g(d,p)和6-311++g(3df,3pd)等为基函数,采用多组态相互作用(MRCI)方法对O2分子最低的两个激发态1Δg1Σ+g的平衡结构、谐振频率和势能曲线进行了计算.并选用Murrell-Sorbie势能函数对曲线进行拟合,利用拟合的参数值计算出了力常数和光谱数据.结果表明计算值与实验值符合较好. 关键词: MRCI 势能函数 力常数 光谱数据  相似文献   

4.
杜泉  王玲  谌晓洪  高涛 《物理学报》2006,55(12):6308-6314
用密度泛函B3LYP/6-311++G(d,p)方法和相对论有效实势(Lanl2dz基组)对VOn±(n=0,1,2)分子离子的势能函数及光谱常数进行了分析. 结果表明它们都能稳定存在, 其基态电子状态分别是:4Σ(VO2-), 3Σ(VO-), 4Σ(VO), 3Σ(VO+)和2Σ(VO2+). 其中VO2-和VO2+的势能函数曲线呈“火山口”型, 属于亚稳态分子离子. 用七参数Murell-Sorbie势拟合VO2-和VO2+分子亚稳态双原子分子离子势能函数, 发现其拟合曲线与势能函数曲线符合得很好. 同时,讨论了电荷对势能函数和能级的影响. 关键词: 分子离子 密度泛函理论 势能函数 能级  相似文献   

5.
利用QCISD(T),SAC-CI方法和cc-pVQZ,aug-cc-pVTZ,6-311++G及6-311++G(3df,2pd)基组,对MgH分子的基态X2Σ+,第一简并激发态A2Π和第二激发态B2Σ+的结构进行优化计算.通过对4个基组计算结果进行比较,得出6-311++G(3df,2pd)基组为最优基组.使用 关键词: 分子结构与势能函数 激发态 Murrell-Sorbie函数 C6函数')" href="#">Murrell-Sorbie+C6函数  相似文献   

6.
王庆美  任廷琦  朱吉亮 《物理学报》2009,58(8):5266-5269
采用量子力学从头计算方法,运用单双取代二次组态相互作用和单双(三)取代二次组态相互作用并结合LanL2DZ基组,计算优化了BiH(D,T)分子基态X3Σ的结构和离解能.并采用最小二乘法拟合改进的Murrell-Sorbie 函数得到了相应的势能函数.计算得到的光谱常数与实验光谱数据符合很好. 关键词: BiH(D T)分子基态 势能函数 Murrell-Sorbie函数  相似文献   

7.
刘慧  邢伟  施德恒  朱遵略  孙金锋 《物理学报》2011,60(4):43102-043102
利用内收缩多参考组态相互作用方法和价态范围内的最大相关一致基aug-cc-pV6Z, 在0.05—0.60 nm的核间距范围内计算了CS+离子X2Σ+和A2Π态的势能曲线. 利用CS+离子的势能曲线并在同位素质量修正的基础上, 拟合出了X2Σ+和A2Π态的同位素离子1 关键词: 同位素识别 势能曲线 光谱常数 分子常数  相似文献   

8.
邢伟  刘慧  施德恒  孙金锋  朱遵略 《物理学报》2013,62(4):43101-043101
采用Davidson修正的内收缩多参考组态相互作用方法(MRCI+Q)及相关一致基aug-cc-pV5Z和aug-cc-pVQZ分别计算了SiSe分子X1Σ+A1Π电子态的势能曲线. 为提高势能曲线的计算精度, 利用两点总能量外推公式, 将两个电子态的势能曲线外推至完全基组极限, 并对其进行了标量相对论修正, 相对论效应是在cc-pV5Z基组水平下使用三级Douglas-Kroll-Hess哈密顿算符计算的. 利用MRCI+Q/Q5+DK理论水平的势能曲线获得了这两个态的光谱常数(Te, De, Re, ωe, ωexe, ωeye, Beαe)和J=0时前30个振动态的BυDυ等分子常数. 其值与已有的实验结果非常一致. 本文得到的光谱常数和分子常数达到了很高精度, 能为进一步的光谱实验和理论研究提供可靠参考. 关键词: 势能曲线 基组外推和标量相对论修正 光谱常数 分子常数  相似文献   

9.
钱琪  杨传路  高峰  张晓燕 《物理学报》2007,56(8):4420-4427
采用从头计算的多参考组态相互作用方法和含扩散基的3个基组aug-cc-PVXZ (X=D,T,Q) 计算了SO和ClO分子及其分子离子的势能曲线,确定了平衡几何结构、离解能,并采用Feller拟合递推方法得到了基函数为无穷大计算水平值. 确定了SO,ClO+,ClO-分子离子的基态. 通过Murrell-Sorbie势能函数和最小二乘法拟合得到了解析势能函数. 基于所得的势能函数,通过解核运动的薛定谔方程得到振 关键词: 多参考组态相互作用 势能曲线 解析势能函数 光谱常数  相似文献   

10.
王兴炜  宋晓书 《计算物理》2021,38(6):729-734
采用高精度的内收缩多参考组态相互作用方法(icMRCI)计算OH+离子基态和低激发态的势能曲线和A3П-X3Σ-跃迁体系的跃迁偶极矩。计算过程中考虑了能量的Davidson修正(+Q)效应和标量相对论修正。根据势能曲线,通过求解核的一维Schrödinger方程得到OH+的光谱参数。通过计算A3П-X3Σ-体系的跃迁偶极矩研究这一跃迁体系的Einstein系数、F-C因子。研究了A3П(ν'=0~6)态的跃迁辐射寿命,结果显示其数量级为10-6 s。  相似文献   

11.
Highly correlated ab initio calculations were performed for accurate determination of γ (A2Σ+-X2П) and β (B2П-X2П) band systems of NO molecule. Highly accurate multi-reference configuration interaction approach was used to investigate the potential energy curves (PECs) and transition dipole moment curves. We correctly and fully described their diffuse wave functions by the obvious balance between the valence and Rydberg character of the X2П, A2Σ+, B2П, C2П and D2Σ+ states. The PECs of the three states (X2П, A2Σ+ and B2П) by using the aug-cc-pV5Z (aV5Z) basis set for N and O atoms agreed well with the Rydberg–Klein–Rees potential. Moreover, the Einstein A coefficients were calculated to predict the lifetimes, where the vibrational bands included v′ = 0–8, v″ = 0–29 for γ system and v′ = 0–11, v″ = 0–31 for β system. The spectral line intensities of the γ and β systems for atmosphere and high temperature were provided.  相似文献   

12.
利用密度泛函B3P86方法,分别选用STO-3G,D95**,6-311G,6-311++G,6-311++G**,cc-PVTZ基组对SiO分子基态(X1Σ+)进行结构优化计算.通过比较得出,cc-PVTZ基组为对SiO分子基态(X1Σ+)进行结构优化最优基组的结论.使用密度泛函B3P86方法,选用cc-PVTZ基组进 关键词: B3P86 SiO 势能函数 光谱常数  相似文献   

13.
刘玉芳  贾毅 《中国物理 B》2011,20(3):33106-033106
This paper calculates the equilibrium internuclear separations, the harmonic frequencies and the potential energy curves of the X^2∑+, A^2П and B^2∑+ states of the CP radical by the highly accurate valence internally contracted multireference configuration interaction method with correlation-consistent basis sets (aug-cc-pV6Z for C atom and aug-cc-pVQZ for P atom). The potential energy curves are all fitted with the analytic potential energy function by the least-square fitting. Employing the analytic potential energy function, we determine the spectroscopic constants (Be, αe and ωeχe) of these states. For the X2∑+ state, the obtained values of De, Be, αe, ωeχe, Re and ωe are 5.4831 eV, 0.792119 cm-1, 0.005521 cm-1, 6.89653 cm-1, 0.15683 nm, 12535.11 cm-1, respectively. For the A2H state, the present values of De, Be,αe, ωeχe, Re and We are 4.586 eV, 0.703333 cm-1, 0.005458 cm-1, 6.03398 cm-1, 0.16613 nm, 1057.89 cm-1, respectively. For the B2E+ state, the present values of De, Be, αe, ωeχe, Re and We are 3.506 eV, 0.677561 cm-1, 0.00603298 cm-1, 5.68809 cm-1, 0.1696 nm, 822.554 cm-1, respectively. For these states, the vibrational states with the rotational quantum number J equals zero (J = 0) are studied by solving the radial nuclear Schr6dinger equation using the Numerov method. For each vibrational state, the vibrational level, the classical turning points, the rotational inertial and the centrifugal distortion constants are calculated. Comparison is made with recent theoretical and experimental results.  相似文献   

14.
Four low-lying electronic states of the BBr molecule, including Σ+ symmetry and Π symmetry with singlet and triplet spin multiplicities, have been studied using the complete active space self-consistent-field method followed by multi-reference single and double excitation configuration interaction calculation. For the ground state, four isotopes (11B79Br, 11B81, 10B79Br, 10B81Br) of the BBr molecule have been studied, since their experimental spectroscopic constants and ro-vibrational energy levels are abundant. For the three excited states, just the most natural abundance isotope–11B79Br–is investigated. The spin–orbital coupling effect for the a3Π state is also considered. Finally, the analytical potential energy functions of these states are fitted except for the 3Σ+ state because its potential well is too shallow to be fitted with available functions. These results have been compared in detail with those of the investigations reported in the literature.  相似文献   

15.
张小妞  施德恒  朱遵略  孙金锋 《中国物理 B》2010,19(12):123501-123501
The potential energy curve (PEC) of HI(X1Σ+) molecule is studied using the complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration interaction approach at the correlation-consistent basis sets, aug-cc-pV6Z for H and aug-cc-pV5Z-pp for I atom. Using the PEC of HI(X1Σ+), the spectroscopic parameters of three isotopes, HI(X1Σ+), DI(X1Σ+) and TI(X1Σ+), are determined in the present work. For the HI(X1Σ+), the values of D0, De, Re, ωe, ωeχe, αe and Be are 3.1551 eV, 3.2958 eV, 0.16183 nm, 2290.60 cm-1, 40.0703 cm-1, 0.1699 cm-1 and 6.4373 cm-1, respectively; for the DI (X1Σ+), the values of D0, De, Re, ωe, ωeχe, αe and Be are 3.1965 eV, 3.2967 eV, 0.16183 nm, 1626.8 cm-1, 20.8581 cm-1, 0.0611 cm-1 and 3.2468 cm-1, respectively; for the TI (X1Σ+), the values of D0, De, Re, ωe, ωeχe, αe and Be are of 3.2144 eV, 3.2967 eV, 0.16183 nm, 1334.43 cm-1, 14.0765 cm-1, 0.0338 cm-1 and 2.1850 cm-1, respectively. These results accord well with the available experimental results. With the PEC of HI(X1Σ+) molecule obtained at present, a total of 19 vibrational states are predicted for the HI, 26 for the DI, and 32 for the TI, when the rotational quantum number J is equal to zero (J = 0). For each vibrational state, vibrational level G(?), inertial rotation constant B? and centrifugal distortion constant D? are determined when J = 0 for the first time, which are in excellent agreement with the experimental results.  相似文献   

16.
The analytical potential energy functions have been calculated for the ground state X1Σ+g and four excited electronic states a1Πg, A3Σ+u, B3Σ?u and B3Πg of N2 molecule using the algebraic and energy-consistent methods (AM-ECM). Based on our previously published full AM vibrational energies and spectroscopic constants, the low-lying force constants fn, the expansion coefficients an and the variational parameters λ in the AM–ECM potentials are determined for these states. The computed AM–ECM potential energy curve of each state is in excellent agreement with the experimental data and better than other analytical potentials.  相似文献   

17.
The potential energy curves of the low-lying electronic states of BeH+ molecular ion are performed by using highly accurate multi-reference configuration interaction with AV5Z basis sets for H atom and ACV5Z basis set for Be atom, 1s inner shell of Be is considered as the core orbit and the active orbit, respectively, which are used to characterise the spectroscopic properties of a manifold of singlet and triplet states. Fourteen electronic states correlated with eight dissociation channels are investigated, we have found that the a3Σ+ and c3Σ+ both are bound states, the 33Σ+ possesses double wells, and the C1Σ+, 33Σ+, 23Π, 21Π, 11Δ, 13Δ, 23Δ and 21Δ states are studied for the first time. Transition dipole moment, Franck–Condon factors qυ′υ and Einstein coefficients Aυ′υ for A1Σ+–X1Σ+, 21Π–B1Π, c3Σ+–a3Σ+ and b3Π–a3Σ+ systems have been calculated. Radiative lifetime of A1Σ+–X1Σ+ band system has also been determined.  相似文献   

18.
Valence and high electronic states of PN have been calculated with accurate quantum chemistry methods. The variety of theoretical methods used includes complete active space self-consistent field, multireference configuration interaction and the newly developed explicitly correlated coupled cluster methods. The large correlation-consistent atomic orbitals basis sets AVQZ, AV5Z and AV(5+d)Z are used for the potential energy curves calculations in the bonding and long-range regions. The spectroscopic constants (Re, Be, ωe, ωexe, αe, De, Te) and the vibrational levels of the bound valence states (X1Σ+, A1Π, a3Σ+, d 3Δ, e3Σ?, C1Σ?, b3Π, D 1Δ and E1Σ+ and some higher bound states) are determined and compared with experimental findings when available. Significant spin–orbit interactions between triplet states and A1Π and E1Σ+ excited states are found near the crossing points of the potential energy curves and could explain predissociation phenomena and the perturbations of the vibrational levels experimentally observed for PN in their A1Π and E1Σ+ states.  相似文献   

19.
采用包含Davidson修正的多参考组态相互作用(MRCI+Q)方法结合6-311++G(3df,3pd)基组计算了LiC分子基态(X4Σ-)以及五个低电子激发态(a2Π,b2Δ,c2Σ-,d2Σ+,A4Π)的势能曲线.将得到的势能曲线拟合到Murrell-Sorbie解析势能函数形式,确定了对应态的平衡结构Re、谐振频率ωe和离解能De等光谱数据,计算值与仅有的几个其他结果进行了比较.通过求解核运动的薛定谔方程首次报道了LiC分子几个低电子态在J=0下的振动能级、转动惯量和六个离心畸变常数(Dν,Hν,Lν,Mν,Nν和Oν).  相似文献   

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