自由基CH和CH_2的基态结构与势能函数

选用OCSD(T)/Aug-cc-PV5Z方法,对CH分子基态的平衡几何进行了优化计算,得到了对应的计算结果.运用含微扰的二次组态相关方法,选用CC-PV5Z基组对CH2分子的基态平衡几何进行了优化计算,得到的结果是:该分子的基态结构为C2v构型,电子态为X3B1,平衡核间距RCH=0.10769nm,键角∠HCH=133.707°,离解能De=5.3277eV,基态振动频率ν1(a1)=1094.24cm-1,ν2(a1)=3144.91cm-1,ν3(b2)=3373.63cm-1.采用多体项展式理论推导了CH2分子基态的解析势能函数,其等值势能图准确再现了CH2分子的结构特征及其势阱深度与位置.在分析讨论势能面的静态特征时,得到了CH H→CH2反应中存在的两个对称鞍点,其活化能为0.13124kJ/mol.     

用耦合簇理论及系列相关一致基研究基态SH+ 和 SD+ 的光谱常数*

利用耦合簇理论CCSD(T)和相关一致基组cc-pVXZ和aug-co-pVXZ(X=2,3,4,5)计算了SH 和SD 的基态平衡几何re、谐振频率ωe和离解能De.计算结果表明,所用基组越大,得到的结果与实验值之间的差别就越小,因此我们选用了大基组aug-cc-pV5Z在0.07～2.50 nm的核间距范围内对SH 和SD 的基态进行单点能计算,并将计算结果拟合成了Murrell-Sorbie函数.利用得到的解析势能函数,计算了SH 和SD 的其余3个光谱常数(ωexe,αe和Be),其结果与实验值符合得相当好.     

基于反射太阳光反演气溶胶光学厚度和有效半径

根据太阳光的极化特性,提出了一种利用单波长太阳光遥感反演球形水凝物气溶胶光学厚度和有效半径的方法.根据矢量辐射传输理论,利用累加法,计算了λ=0.75μm(可见光)和3.3μm(近红外)两种波长太阳光入射时气溶胶的反射矩阵.气溶胶的有效半径为0.01—1.5μm,光学厚度为0.05—1.利用计算机模拟了反演过程,结果表明,当粒子的有效半径小于0.4μm时可以利用可见光波段进行反演;当粒子有效半径大于1.0μm时可以利用近红外波段反演;在0.4—1.0μm之间,利用这两个波段均可以得到精确性很 关键词： 光学厚度 有效半径 极化 反演     

利用硼泥制备三水碳酸镁晶须

用工业硫酸处理硼泥,经过除杂得到纯净的硫酸镁溶液,以碳酸钠为沉淀剂,以磷酸氢二钠为添加剂,制备MgCO3·3H2O晶须.利用IR,XRD,TC,TEM等对产物进行表征,探索了工业硫酸处理硼泥的最佳条件,考察了反应温度、搅拌时间对产物的影响.结果表明,利用硼泥制备三水碳酸镁晶须的最佳反应条件是:硼泥与工业硫酸的固液比1∶2.5,300℃煅烧1.8h,用氨水调节pH =7.5除去杂质离子,得到纯净的硫酸镁溶液,50℃滴加碳酸钠搅拌反应50 min,陈化1h过滤,50℃烘干3h.     

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.     

学生在化学题解答中的几种心理致误因素浅析

近几年我省高考化学科试卷质量分析反应出考生错解、误解试题的现象比较严重。我认为,这不仅是学生基础知识不牢固、不会应用所学知识解决问题这一因素的影响,学生的心理障碍对考试效果的影响也不容忽视。     

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 $J=0$.