Investigations of spectroscopic parameters and molecular constants for X1Σg+, w3Δu, and W1Δu electronic states of P2 molecule

The potential energy curves (PECs) of three low-lying electronic states (X¹Σ_g⁺, w³Δ_u, and W¹Δ_u)of P₂ molecule are investigated using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent basis set in the valence range. The PECs of the electronic states involved are modified by the Davidson correction and extrapolated to the complete basis set (CBS) limit. With these PECs, the spectroscopic parameters of the three electronic states are determined and compared in detail with the experimental data. The comparison shows that excellent agreement exists between the present results and the available experimental data. The complete vibrational states are computed for the w³Δ_u, and W¹Δ_u electronic states when the rotational quantum number J equals zero and the vibrational level G(v), the inertial rotation constant B_v, and the centrifugal distortion constant D_v of the first 30 vibrational states are reported, which accord well with the experimental data. The present results show that the two-point extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.     

boldmath B3Σu-–X3Σg- transition in selenium dimer: ab initio multireference configuration interaction calculations

Theoretical investigation of low-lying electronic states and B³Σ_u^-–X³Σ_g^- transition properties of selenium dimer using size-extensivity singly and doubly excitation multireference configuration interaction theory with nonrelativistic all-electron basis set and relativistic effective core potential plus its split valence basis set is presented in this paper. The spectroscopic constants of ten low-lying Λ-S bound states have been obtained and compared with experiments. Spin-orbit calculations for coupling between B³Σ_u^- sates and repulsive ¹Π_u, ⁵Π_u states have been made to interpret the predissociation mechanisms of the B³Σ_u^- state. The lifetimes of B³Σ_u^- (v=0～6) have been calculated with scalar relativistic effects included or excluded, respectively, and reasonably agree with experimental values.     

A STUDY OF RAMAN SCATTERING AND INFRARED ABSORPTION SPECTRUM IN A NEW SERIES OF MERCURY-BASED HIGH-Tc SUPERCONDUCTOR (Hg,Mo)Sr2(Y1-xCax)Cu2O6+δ

Lattice vibrations of the (Hg,Mo)Sr₂(Y_1-xCa_x)Cu₂O_6+δ—a new series of mercury-based high-T_c superconductor are analyzed with the aid ofgroup theory. The vibrations of species are given. They are 4A_1g+ B_1g+ 5E_g+ 7A_2u + B_2u+ 8E_u. The 4A_1g, B_1g and 5E_g modes are Ramma active, the 6A_2u and 7E_u are infrared active. Phonon vibration characteristics of the samples are studied using Raman scattering and infrared absorption spectra. The experimental results show that the typical phonon vibrational modes appear mainly at 145, 320, 440, 578, 592 and 645cm^-1, The intensities of the 145, 320, 440, 578 and 645 peaks decrease with increasing Ca content x and the position of 645 peak moves to higher wavenumber slightly. In this article, the phonan modes are assigned and their variation behavior with increasing Ca content x are discussed.     

OPTICAL-OPTICAL DOUBLE-RESONANCE EXCITATION SPECTRA OF THE (6d)1Πg, (7d)1Πg HIGH-LYING RYDBERG STATES IN Na2

Two ¹Π_g states of Na₂ for v≤13 have been observed by using optical-optical double resonance (OODR) fluorescence excitation spectroscopy. The intermediate levels in B¹Π_u state are identified by the numerical calculations with the molec-ular constants for B¹Π_u←X¹Σ_g⁺ transitions and confirmed by the complemen-tary A¹Σ_g⁺←X¹Σ_g⁺ polarization spectra. Absolute vibrational numberings of the (6d)¹Π_g and (7d)¹Π_g states are determined by comparing the experimental OODR excitation intensities with the simulated Franck-Condon factors. The Dnnham coef-ficients and the Rydberg-Klein-Rees (RKR) potential energy curves of the (6d)¹Π_g, (7d)¹Π_g states are reported.     

He2分子 b3Πg(v=9)态的预解离

利用光外差-浓度调制吸收光谱技术测量了b³Π_g～a³∑_u⁺(9,3)带在12065～12445 cm^-1的光谱,并研究了He₂分子b³Π_g(v=9)态与c³∑_g⁺ 态的预解离相互作用．基于He₂分子c³∑_g⁺ 态的ab initio理论计算势能曲线和b³Π_g态的RKR势能曲线,分析了b³Π_g(v=9)态的预解离机制,并计算了b³Π_g(v=9)态转动能级的预解离线宽,计算结果同实验测量基本一致.     

Cs2 23△1g态碰撞线归属和超精细结构解释

根据最新的Cs₂分子中间态A¹∑⁺_u -b³Πu全局解微扰获得的能级数据, 归属了通过微扰增强红外-红外光学双共振中间态A¹∑⁺_u 到上态2³△_1g的140条碰撞线, 包含之前实验观测到的221条2³△_1g←A¹∑⁺_u← X¹∑⁺_g 双共振跃迁[J. Chem. Phys. 128, 204313 (2008)], 重新计算了2³△_1g态的分子常数和势能曲线(排除54个微扰能级). 本次拟合得到的离心畸变常数和从经验公式计算得到的值相符合. 在亚多普勒激发光谱中,没有分辨出2³△_1g态的超精细结构. 对2³△_1g态的超精细结构进行初步计算,比较实验结果给出解释和说明.     

OCS+分子经由B2∑+←X2∏跃迁的光解离谱

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∑+←X2∏_3/2(000)和B2∑+←X2∏_1/2(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)←X2∏_1/2(000)跃迁的谱峰, 而观察不到B2∑+←X2∏_3/2(000)跃迁的谱峰． 用X2∏电子态的(000)2∏_1/2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}     

二氧化碳分子离子经由Ã2Πu1/2电子态振动能级共振的光解动力学：一项时间切片离子速度成像技术研究

We report on the photodissociation dynamics of CO₂⁺ via its òΠ_u,1/2 state using the scheme of [1+1] photon excitation that is intermediated by the mode-selected òΠ_u,1/2( u1,u2,0) vibronic states. Photodissociation fragment exciation spectrum and images of photofragment CO⁺ have been measured to obtain reaction dynamics parameters such as the available energy and the average translational energy. Combining with the potential energy functions of CO₂⁺, the dissociation mechanism of CO₂⁺ is discussed. The conformational variation of CO₂⁺ from linear to bent on the photodissociation dynamics of CO₂⁺ is verified.     

ANALYSIS OF F′0+u ION-PAIR STATE OF IODINE

The optical-optical double resonant multiphoton ionization (OODR-MPI) technique and the fluorescent excitation spectroscopy technique have been applied to the study of the F′0⁺_u ion-pair state of iodine. This paper presents OODR-MPI spectrum and fluorescent excitation spectrum of I₂ in the region of 54000-55300cm^-1 by the three-photon resonant, two-photon ionization (1+2+2) and (1+(1+1)+2) processes.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

OCS经由F 31Π里德堡态生成CO(X1Σ+)+S(1D2)产物的波长相关性光解离

本文利用时间切片离子速度成像技术在134∽140 nm波段研究了OCS分子经由F 3¹Π里德堡态的真空紫外光解离动力学. 在选取的5个分别对应OCS(F 3¹Π, v₁=0∽4)的伸缩振动激发的光解波长,实验测得了来自CO(X¹Σ⁺)+S(¹D₂)产物通道的SS(¹D₂))实验影像,并获得了总平动能谱和CO(X¹Σ⁺, v)共生产物的振动布居及角分布. 结果分析表明OCS分子解离生成CO(X¹Σ⁺)+S(¹D₂)产物的过程经历了上态F 3¹Π 与C_?v和C_s构型的下电子态间非绝热耦合过程. 实验结果显示了很强的波长相关性：OCS (F 3¹Π, v₁)的较低转动激发态(v₁=0∽2)和较高转动激发态(v₁=3, 4)的CO(X¹Σ⁺)产物的振动布居和角分布具有显著差异,表明该解离过程中具有不同的解离机理. 本结果提供了振动耦合可能对真空紫外光解离动力学产生关键作用的相关证据.     

氮分子离子A2Πu-X2Σ+g 带系转动光谱分析:

利用光外差速度调制分子光谱技术测得氮分子离子A²Π_u-X²Σ⁺_g 带系的(3,1)、(4,2)、(5,3)、(8,5)带的谱线,其中(5,3)带是第一次被指认．利用测得的4个带以及文献中的14个带的谱线进行全局拟合,得到了一系列的分子常数(υ_A=0～9和υ_A=0～5)．     

CuH分子A1∑+态的寿命和预解离研究

A combined cavity ringdown (CRD) and laser induced fluorescence (LIF) spectroscopic study on the A¹∑⁺-X¹∑⁺ transition of CuH has been presented.The CuH molecule,as well as its deuterated isotopologue CuD,are produced in a supersonic jet expansion by discharging H₂(or D₂) and Ar gas mixtures using two copper needles.Different profiles of relative line intensities are observed between the measured LIF and CRD spectra,providing an experimental evidence for the predissociation behavior in the A¹∑⁺ state of CuH.The lifetimes of individual upper rotational levels are measured by LIF,in which the J''-dependent predissociation rates are obtained.Based on the previous theoretical calculations,a predissociation mechanism is concluded due to the strong spin-orbit coupling between the A¹∑⁺ state and the lowest-lying triplet ³∑⁺ state,and a tunneling effect may also be involved in the predissociation.Similar experiments are also performed for CuD,showing that the A¹∑⁺ state of CuD does not undergo a predissociation process.     

Spectroscopic investigations on NO+(x1∑+,a3∑+,A1Ⅱ) ion using multi-reference configuration interaction method and correlation-consistent sextuple b

Three low-lying electronic states (x¹∑⁺,a³∑⁺,and A¹Ⅱ) of NO⁺ ion are studied using the complete active space self-consistent-field (CASSCF) method followed by highly accurate valence internally contracted multi-reference configuration interaction (MRCI) approach in combination of the correlation-consistent sextuple basis set augmented with diffuse functions, aug-cc-pV6Z. The potential energy curves (PECs) of the NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) are calculated. Based on the PECs, the spectroscopic parameters R_e, D_e, ω_e, ω_eχ_e, α _e, B_e, and D₀ are reproduced, which are in excellent agreement with the available measurements. By numerically solving the radial Schrödinger equation of nuclear motion using the Numerov method, the first 20 vibrational levels, inertial rotation and centrifugal distortion constants of NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) ion are derived when the rotational quantum number J is equal to zero (J = 0) for the first time, which accord well with the available measurements. Finally, the analytical potential energy functions of these states are fitted, which are used to accurately derive the first 20 classical turning points when J = 0. These results are compared in detail with those of previous investigations reported in the literature.     

Investigation of the A2Σ- state of CuO by laser-induced fluorescence

The laser-induced fluorescence excitation spectrum of the A²Σ^－X²Π_3/2 transition of CuO in the 540－620nm region has been studied, where the CuO molecule was produced by using the technique of dc discharge reaction under a supersonic condition. We have recorded and rotationally analysed the 0－0, 1－0, 2－0 and 3－0 bands. The rotational constants of the upper state A²Σ^- were determined and vibrational constants improved. In addition, the lifetime measurement for the A²Σ^- state was carried out under the collision-free condition, and the lifetimes obtained are 469±2, 456±2, 488±3 and 490±4ns for v'=0, v'=1, v'=2 and v'=3 levels, respectively.     

LiS分子和离子基态的精确理论研究

Potential energies of LiS(²Π), LiS^-(¹Σ⁺) and LiS⁺(³Σ^-) are calculated by using the multireference configuration interaction method including Davidson correction and the augmented correlation-consistent basis sets aug-cc-PV(X+d)Z (X=T, Q). Such obtained potential energies are subsequently extrapolated to the complete basis set limit. Both the core-valence correction and the relativistic effect are also considered. The analytical potential energy functions are then obtained by fitting such accurate energies utilizing a least-squares fitting procedure. By using such analytical potential energy functions, we obtain the accurate spectroscopic parameters, complete set of vibrational levels and classical turning points. The present results are compared well with the experimental and other theoretical work.     

MgH的A2Π-X2Σ+振动跃迁的Frank-Condon因子和带头

利用激光消融/激光诱导荧光的方法测量了MgH分子A²Π～X²Σ⁺的色散荧光谱, 并通过分析实验光谱获得了MgH分子的A²Π(v′=0)～X²Σ⁺(v〞=0,1)跃迁的弗朗克-康登因子和相应的跃迁频率. 同时也用理论计算方法计算出MgH分子A²Π(v′=0)～X²Σ⁺(v〞=0,1)的弗朗克-康登因子和跃迁频率. 实验结果、理论结果和其他文献中的理论结果是一致的.     

在193 nm关于Si2分子的离子解离动力学的成像研究

在193 nm的单色激光实验中,本文利用时间切片离子速度成像技术,研究了经193 nm双光子电离得到的Si₂⁺的解离反应动力学过程. 根据实验得到的Si⁺离子的速度成像,观测到了两种离子直接解离通道：Si(³P_g)+Si⁺(²P_u)和Si(¹D₂)+Si⁺(²P_u). 电子基态的Si₂分子处于v=0∽5的振动态上,其经过双光子电离后激发到Si₂⁺离子的多个电子激发态势能面,生成主要通道Si(³P_g)+Si⁺(²P_u),其中v=1的解离信号最强. 此外,由于势能曲线2²Π_g与3²Π_g相同对称性引起的避免性势能面交叉,生成次要反应通道Si(¹D₂)+Si⁺(²P_u). 通道Si(¹D₂)+Si⁺(²P_u)的产物亦可以由生成的基态Si₂⁺(X⁴Σ_g^-)吸收一个193 nm光子后解离得到,其对应产物则具有更大的动能.     

二硫化碳分子在204 nm附近的光解离动力学研究：S(3PJ)+CS(X1Σ+)产物通道

本文用时间切片离子速度影像技术研究CS₂分子在204 nm附近的光解离动力学. 在201.36、203.10、204.85和206.61 nm这四个解离波长下,实验清楚地观测到S(³P_J)+CS(X¹Σ⁺)产物通道. 在实验获得的S(³P_J=2,1,0)影像中,对应的CS(X¹Σ⁺)产物的振动态结构得到了部分的分辨. 通过对影像的分析,还获得了解离的总平动能谱以及产物的各项异性参数. 实验观察到的相对小的各项异性参数表明产物更倾向于经历了间接的光解离过程. 这一通道的自旋－轨道禁阻特征也说明了非绝热效应在二硫化碳紫外光解离生成S(³P_J=2,1,0)+CS(X¹Σ⁺)的过程中发挥了重要作用.     

PuO分子X5Σ-态的势能函数及热力学 函数的量子力学计算

The potential energy function for ground state X⁵Σ^- of the PuO molecule was worked out by the quadratic configuration interaction of single and double substitution method, based on the approximation of relativistic effective core potential for Pu atom and all-electron 6-311G^ basis set for O atom. The calculated results for R_e,D_e,B_e,α_e,ω_e and ω_eχ_e are 0.183nm,7.3909eV,0.3365,0.001642,781.15,and 2.77cm^-1,respectively.In addition,the thermodynamic functions ΔH⁰,ΔS⁰,ΔG⁰ and C_p of the PuO(g) in standard state are also calculated,which are -118.88kJ/mol,96.16J/mol^.K,-147.55kJ/mol,and 31.5656J/mol^.K,respectively. All these results are in good agreement with the experimental data.