Quantum stereodynamics study for the reaction F + HD

This paper studies the quantum stereodynamics of the F + HD(υ = 0, j = 0) → HD + F/HF + D reaction at the collision energies of 0.52 and 0.87~kcal/mol. The quantum scattering calculations, based on Stark-Werner potential energy surfaces, show that the differential cross sections for the HF(υ' = 2) + D and DF(υ' = 3) + H channels are consistent with the recent theoretical results. Furthermore, the product rotational angular momentum orientation and alignment have been determined for some selected rovibrational states of the HF + D and DF + H channels.     

icMRCI+Q理论研究BF~+离子电子态的光谱性质和预解离机理

采用考虑Davidson修正的内收缩多参考组态相互作用(icMRCI+Q)方法,结合相关一致基组aug-ccpV5Z和aug-cc-pV6Z,计算了BF+离子前两个离解极限B~+(~1S_g)+(~2P_u)和B+(~3P_u)+F(~2P_u)对应的14个Λ-S态(X~2Σ~+,1~2Π,2~2Π,2~2Σ~+,1~4Σ~+,1~4△,1~4Σ~-,1~2△,1~2Σ~-,3~2Σ~+,1~4Π,2~4Π,2~4Σ~+和3~2Π)和30个Ω态的势能曲线.在势能曲线的计算中,考虑了旋轨耦合效应、核价相关和标量相对论修正以及将参考能和相关能分别外推至完全基组极限.基于得到的势能曲线,获得了束缚和准束缚的12个A-S态和28个Ω态的光谱常数,并且X~2Σ~+态的光谱常数与已有的实验结果符合.此外,计算了BF分子X~1Σ~+态到BF+离子X~2Σ~+,1~2Π和2~2Σ~+态的垂直电离势和绝热电离势,并且BF~+(X~2Σ~+)←BF(X~1Σ~+)的垂直电离势和绝热电离势与相应的实验结果非常符合.由X~2Σ~+,2~2Π,1~4Σ~+,3~2Σ~+和3~2Π态和其他的激发A-S态势能曲线的交叉现象,借助于计算的旋轨耦合矩阵元,首次分析了X~2Σ~+和3~2Π态的预解离机理以及2~2Π(v′≥9),1~4Σ~+(v′≥4)和3~2Σ~+(v′≥4)的振动能级受到其他电子态的微扰.计算了30个Ω态离解极限处的相对能量,并且与实验结果十分符合.最后计算了2~2Π(v′=0—9)—X~2Σ~+,2~2Σ~+(v′=0—2)—X~2Σ~+,(3)1/2—(1)1/2~(势阱一)和(2)3/2(v′=0—9)—(1)1/2~(势阱一)跃迁的Franck-Condon因子、爱因斯坦自发辐射系数和辐射寿命.     

孤子内波导致海洋环境噪声垂直指向性异常分析

依据近场波数积分、远场耦合简正波相结合的二维噪声场模型,侧重理论研究孤子内波所在扇区,环境噪声垂直阵响应的变化,分析了某些孤子内波情形下垂直阵环境噪声水平凹槽变深这一异常现象的原因:孤子内波离垂直阵较近时,远离内波的海面噪声源多,其激发的简正波能量由低号耦合到高号,在垂直阵处高号简正波能量对环境噪声场贡献增大,导致环境噪声水平凹槽加深;对于大尺度、多波包孤子内波,其范围相对较大,内波所在区的局部简正波本征值和本征函数产生的变化影响显著,使低号简正波衰减变快,而高号衰减慢,导致接收阵处高号简正波能量增加,低号简正波变弱,这样,无论孤子内波群靠近或离接收阵远,都将使垂直阵环境噪声水平凹槽加深。      

Elastic scattering of two ground-state N atoms

An interaction potential for an N₂(X¹σ_g⁺) molecule is constructed by using the highly accurate valence internally contracted multireference configuration interaction method and the largest basis set, aug-cc-pV6Z, in the valence range. The potential is used to investigate the elastic scattering of two N atoms at energies from 1.0× 10^-11 to 1.0× 10^-4 a.u. The derived total elastic cross sections are very large and almost constant at ultralow temperatures, and the shape of total elastic cross section curve is mainly dominated by the s-partial wave at very low collision energies. Three shape resonances are found in the total elastic cross sections. Concretely, the first one is very sharp and strong. It results from the g-partial-wave contribution and the resonant energy is 3.645× 10^-6 a.u. The second one is contributed by the h-partial wave and the resonant energy is 1.752× 10^-5 a.u. This resonance is broadened by those from the d- and f-partial waves. The third one comes from the l = 6 partial wave contribution and the resonant energy is 3.522× 10^-5 a.u. This resonance is broadened by those from the g- and h-partial waves. The N₂(X¹σ_g⁺) molecular parameters, which are determined at the current theoretical level, achieve very high accuracy due to the employment of the largest correlation-consistent basis set in the valence range.     

Investigations on spectroscopic parameters, vibrational levels, classical turning points and inertial rotation and centrifugal distortion constants for the X1∑+g state of sodium dimer

The density functional theory (B3LYP, B3P86) and the quadratic configuration-interaction method including single and double substitutions (QCISD(T), QCISD) presented in Gaussian03 program package are employed to calculate the equilibrium internuclear distance $R_{\rm e}$, the dissociation energy $D_{\rm e }$ and the harmonic frequency $\omega _{\rm e}$ for the $X{}^{1}\Sigma^{ + }_{\rm g}$ state of sodium dimer in a number of basis sets. The conclusion is gained that the best $R_{\rm e}$, $D_{\rm e}$ and $\omega _{\rm e}$ results can be attained at the QCISD/6-311G(3df,3pd) level of theory. The potential energy curve at this level of theory for this state is obtained over a wide internuclear separation range from 0.16 to 2.0~nm and is fitted to the analytic Murrell--Sorbie function. The spectroscopic parameters $D_{\rm e}$, $D_{0}$, $R_{\rm e}$, $\omega _{\rm e}$, $\omega _{\rm e}\chi _{\rm e}$, $\alpha _{\rm e}$ and $B_{\rm e}$ are calculated to be 0.7219~eV, 0.7135~eV, 0.31813~nm, 151.63~cm$^{ - 1}$, 0.7288~cm$^{ - 1}$, 0.000729~cm$^{ - 1}$ and 0.1449~cm$^{ - 1}$, respectively, which are in good agreement with the measurements. With the potential obtained at the QCISD/6-311G(3df,3pd) level of theory, a total of 63 vibrational states is found when $J=0$ by solving the radial Schr\"{o}dinger equation of nuclear motion. The vibrational level, corresponding classical turning point and inertial rotation constant are computed for each vibrational state. The centrifugal distortion constants ($D_{\upsilon }\, H_{\upsilon }$, $L_{\upsilon }$, $M_{\upsilon }$, $N_{\upsilon }$ and $O_{\upsilon })$ are reported for the first time for the first 31 vibrational states when $J=0$.     

分布式光纤测温在蒸汽管路监测上的应用及滤波北大核心CSCD

面对热电厂中存在的高温蒸汽管路输送距离长、泄漏点难以寻找的问题,搭建分布式光纤测温系统,对蒸汽管路的温度场进行监控。系统根据拉曼散射原理解调出了管道沿线铺设光缆中反射光信号内含有的温度信息,并根据光时域反射技术将温度与对应的管道进行位置匹配。同时系统通过卡尔曼滤波算法对解调出的温度信号进行了滤波,结果证明卡尔曼滤波能够将系统测量的温度波动降低至1℃。     

基于表面增强拉曼光谱的市售氢溴酸右美沙芬止咳糖浆的生产溯源和产品质控研究

药物生产过程中的质量控制与市售成品药物的生产溯源是保障消费者用药安全的关键环节。目前常见的药物分析方法存在操作繁琐或抗干扰能力差等问题，实现高效快速的药物分析仍是尚未解决的难题。基于表面增强拉曼光谱（SERS）的指纹图谱高分辨能力和痕量检测灵敏度，结合主成分分析（PCA）方法对弱信号的准确识别和分类能力，该文开展了氢溴酸右美沙芬止咳糖浆成品药的产地溯源（不同厂家）和产品质控（某一厂家）的可行性研究。通过支持向量机（SVM）分类算法验证，SERS-PCA方法对不同厂家分类的准确度为100%。研究结果为推动“SERS+化学计量学”在药物分析领域的实际应用提供了一种切实可行的参考方案。     

N2同位素分子X1Σ+g态的光谱常数与分子常数

利用内收缩多参考组态相互作用方法和核价相关一致极化基aug-cc-pCV5Z在0.04-0.54 nm的核间距范围内计算了N2分子X1Σ+g态的势能曲线. 利用这一势能曲线并在同位素质量识别的基础上, 拟合出了同位素分子14N2(X1Σg+), 15N2(X1Σg+)和14N15N(X1Σg+)的光谱常数(D0, De, Re, ωe, ωexe, αe和Be)和无转动时的振动能级G(υ)、惯性转动常数Bυ和离心畸变常数Dυ等分子常数. 这些结果与已有的实验值十分一致.     

利用盲反卷积和混沌振子增强船舶辐射噪声解调线谱

针对经典解调方法中心频率、带宽选择困难和解调线谱受带外噪声干扰难以分辨等问题,提出采用盲反卷积和混沌振子方法抑制带外噪声,增强船舶噪声解调线谱。该方法通过Duffing振子预检宽带船舶噪声低频弱周期信号,随后将相应频率作为最小噪声幅值比反卷积(MNAD)方法的先验参数,利用MNAD方法自适应搜索解调频带得到可清晰分辨的高信噪比解调线谱。仿真和实测数据分析表明,该方法较经典解调方法和其他盲反卷积方法,可获取更佳的中心频率和滤波带宽,所得解调线谱的窄带信噪比DF值最高。     

理论研究BeS(X1∑+)的光谱常数及分子常数

采用Davidson较正的内收缩多参考组态相互作用方法(MRCI+Q)结合相关一致五重基cc-pV5Z在二阶Douglas-Kroll Hamiltonian近似下,计算了BeS分子X1∑+态的势能曲线.对势能曲线进行核价相关效应修正计算,得到了同时含有核价相关效应修正及相对论效应的势能曲线.拟合修正的势能曲线,获得BeS(X1∑+)的光谱常数Rc,wc,ωcxc,wcyc,Bc,ac,,β和D0,分别为:0.17429 nm,997.06 cm-1,6.1056 cm-1,0.0041 cm-1,0.7893 cm-1,0.006657 cm-1,6.8002×10-9 cm-1和4.2609 eV.与已有的实验结果及其它理论结果的比较表明,本文BeS(X1∑+)的光谱常数的计算结果达到了较高的精度.通过求解双原子分子核运动的径向Schr(o)nger方程,找到了非转动BeS(X1Σ+)的前40个振动态.针对每一振动态还分别计算了相应的振动能级、惯性转动常数和离心畸变常数等分子常数.