用神经网络方法拟合的反应体系H+CH4→H2+CH3的一个全域势能 (cited:12)

利用神经网络方法,基于47783个高精度从头算能量点构建了反应体系H+CH₄→H₂+CH₃的一个全域势能面．通过大量的准经典轨线以及量子散射计算测试了势能面的收敛性质．这个势能面对于拟合过程以及从头算点的数目都已经完全收敛,拟合误差很小且比Shepard插值的势能面计算速度更快,代表了此标志性多原子反应体系最好的势能面．     

N+ND反应的量子力学速率常数

在两个耦合的势能面1²A′和2²A′上对N+ND反应进行了非绝热量子动力学研究. 计算了N+ND→N₂+D反应和N′+ND→N′D+N反应在5 meV～1.0 eV碰撞能的反应几率和积分截面. 结果发现N+ND→N₂+D反应是N+ND反应的主要反应通道.另外,计算了N+ND→N₂+D 反应的速率常数.     

H+Br2→HBr+Br反应的态-态量子动力学研究

H原子与卤素气体(F₂,Cl₂,Br₂)的反应是典型的轻-重-重原子-双原子反应. 对于研究化学激光的基本反应途径十分重要. 之前所有的实验结果都表明,H+Br₂→HBr+Br反应的势垒高度很小,甚至是负值. 本文基于11698个UCCSD(T)/CBS水平的从头算能量点,用FI-NN方法构建了HBr₂体系的精确全维全域势能面,还包括了Br原子²P_3/2轨道的自旋-轨道耦合. 势能面有一个下沉的势垒(-0.351 kcal/mol}),放热(ΔH₀=-41.265 kcal/mol) 和实验值吻合的很好,在这个势能面上应用含时波包方法计算了H+Br₂→HBr+Br反应的态-态积分和微分截面. 对初始基态反应,产物HBr(v′=2,3,4)态在所考虑的整个能量范围内占主导地位,说明HBr是振动态布居反转的. 温度300 K时,计算的产物振动分布在$v$$''$=3有最大值,在v′=0,1的分布可以忽略不计,这与Setser及合作者和Polanyi及合作者的实验结果相一致. 超过一半的总可用能量进入到产物的内部运动中,这其中大部分进入到振动中. 计算表明,反应物Br₂的初始转动激发对产物振转态分布和微分截面影响很小,而初始振动激发则有一定影响. 在低能区域,初始振动激发到v₀=5态很明显的增强了产物的振动激发. 在初始基态和初始转动激发态下,碰撞能量到0.5 eV的微分截面在后向达到峰值,但随着碰撞能量的增加,角分布的宽度显著增加. 对于初始振动激发态,产物微分截面的结构较为复杂,对高振动激发态产物有很强的前向散射峰.     

Superacid Catalyst SO42-/ZrO2-La2O3 Prepared by Ultrasonic Co-precipitation and Low Temperature Aging

低温陈化超声波共沉淀法制得SO₄^2-/ZrO^2-La₂O₃前驱体, 经H₂SO₄处理, 在不同温度下焙烧得到纳米晶催化剂SO₄^2-/ZrO^2-La₂O₃;用Hammett指示剂法测定其酸性. 用XRD、BET、TEM、IR和XPS对样品进行表征,其催化活性用醋酸和甘油的酯化反应进行了评价. 结果表明经超声波搅拌和低温(-15 ºC)陈化,650 ºC焙烧4 h得到的固体超强酸表现出较高催化活性.     

Ar2-Ne聚合物的三维势能面和束缚态

使用单双激发并对三重激发作微扰处理的耦合簇方法计算了Ar₂-Ne聚合物的三维势能面. 使用的基组是aug-cc-pVqz并包括3s3p2d2f1g中点键函数. 用二维模型势对7个Ar₂键长值的每一个对应的二维格点(R,θ)上的能量进行了拟合. 再将7个二维模型势通过对(r—re) 的六次多项式内插得到三维势能面,并用于随后的振转能级计算,所得到的跃迁频率、光谱常数等与相应的实验结果进行了比较.     

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.     

Pr3+离子单掺LiLuF4单晶的坩埚下降法生长及光谱性能研究

本文应用坩埚下降法技术在全密封铂金坩埚条件下生长了不同Pr³⁺离子掺杂浓度的高质量LiLuF₄单晶. 测定了单晶体从420 nm至500 nm的激发光谱. 在446 nm光激发下,观察到单晶体480 nm(³P₀→³H₄)蓝色发射带、522 nm(³P₁→³H₅)绿色发射及605 nm(¹D₂→³H₄)的红色发射,其对应的平均寿命分别为38.5、37.3和36.8 μs. 其荧光寿命明显大于Pr³⁺掺杂的氧化物单晶. 同时研究了激发波长和掺杂浓度对发射强度以及色度坐标的影响. 获得最佳的Pr³⁺浓度为∽0.5 mol%,并分析了环境温度从298 K 到443 K变化对荧光强度的影响. 结果表明随着温度的增加,荧光强度逐步变弱,其中³P₀→³H₄(480 nm)能级跃迁受温度影响最大,其次是³P₁→³H₅和¹D₂→³H₄.     

神经网络方法构建苯硫酚三维非绝热势能面

本文利用神经网络方法构建了苯硫酚三维的基态(S₀)绝热势能面以及激发态¹ππ^*和¹πσ^*耦合的非绝热势能面. 特别地，¹ππ^*和¹πσ^*非绝热势能面的透热化是通过神经网络拟合实现的，拟合仅基于其绝热势能，但对非绝热势能矩阵的非对角元施加了对称性的正确限制. 神经网络拟合的3个态的势能面的拟合均方根误差都非常小(<4 meV)，体现了神经网络方法的高精度. 在神经网络构建的势能面上计算得到了S₀态的低位能级和S₁ 态0⁰ 的寿命，结果均与早前非绝热势能面上的结果吻合，验证了神经网络方法构建的绝热和非绝热势能面的高精度和可靠性.     

CH4-Ne体系的三维从头算势能面与光谱的模拟

本文在从头算CCSD(T)/AVXZ(X=T,Q)水平上计算了CH₄-Ne体系的三维势能面,同时在基组中加入了键函数,并且将基组外推到完全基组极限水平. 通过最小二乘法拟合摩斯长程势能函数形式,获得了三维分析势能面,其中对664个从头算格点的拟合的标准偏差仅为0.042 cm^-1. 随后,采用径向离散变量表象和角度有限基组表象相结合的杂化基函数方法,并基于Lanzcos迭代的方法获得了CH₄-Ne体系的振转能级,所预测的红外光谱与实验值非常吻合. 本文首次给出了CH₄-Ne体系的微波光谱数据. CH₄-Ne体系三维摩斯长程势能面分析的表达式为今后CH₄在Ne团簇动力学性质以及其碰撞诱导吸收光谱的研究中奠定了基础.     

He-H2S复合物的六维从头算势能面和束缚态

采用[CCSD(T)]-F12a/aug-cc-pVTZ方法，同时在基组中引入中心键函数(3s3p2d1f1g)构建了He-H$_2$S复合物的高精度六维势能面. 除分子间振动坐标，同时考虑了H₂S分子内的v₁对称伸缩振动Q₁正则模、v₂弯曲振动Q₂正则模和v₃反对称伸缩振动Q₃正则模三种振动模式. 将计算得到的六维势能面在Q₁，Q₂和Q₃方向上分别做积分得到H₂S单体分别处于振动基态、v和v₃激发态下的He-H₂S的三个振动平均势能面. 计算结果表明，每个平均势能面都有一个T形全局极小值、一个平面局部极小值、两个平面内鞍点和一个平面外鞍点. 全局极小值的几何构型位于R=3.46 ?，θ=109.9°和φ=0.0°，势阱深度为35.301 ^-1. 在径向部分采用离散变量表象法和角度部分采用有限基组表象法并结合Lanczos循环算法计算了He-H₂S的振转能级和束缚态. 计算发现He-(para-H₂S)在H₂S的v₂和v₃区域的带心位移分别为0.025 cm^-1和0.031 cm^-1，而He-(ortho-H₂S)的带心位移分别为0.041 cm^-1和0.060 cm^-1，都表现为蓝移.     

Ba原子6s6p1P1←6s6s1S0跃迁的光腔衰荡光谱

建立了一套光腔衰荡原子束吸收光谱测量装置,并对Ba原子的6s6p¹P₁←6s6s¹S₀吸收谱线用光腔衰荡光谱方法进行了测量,得到了Ba原子在553.548nm不同温度下的吸收谱线线型.实验结果表明,该装置测量吸收灵敏度达到6×10^-7. 关键词： 光腔衰荡 吸收光谱 Ba原子     

Ion-electron coincidence study of the thermal He(23S) + H2 Penning reaction

A new Penning-electron-Penning-ion coincidence method is described. It is applied to the study of the thermal reaction of He(2³S) with H₂. The main results reported are separate electron energy spectra that are coincident with the three different ions formed: HeH₂⁺, HeH⁺ and H₂⁺. Based on these results it is shown that the Penning reaction of the He(2³S)/H ₂ system proceeds in two well-separated steps: (i) ionization at distances R (HeH₂) ? 6a₀ in which H₂⁺ (v) is formed in different vibrational states; and (ii) reactive collision of H₂⁺ (v) with He. For the second step the variation of the branching ratios with vibrational quantum numbers v = 0 to v = 10 is derived, and it is shown that these branching ratios may be regarded as relative vibrational-energy-dependent cross-sections for the collision of H₂⁺ (v) with He at an average relative kinetic energy of ～20 meV.     

Electronic energy transfer from Cd(53P1 to Popop vapor

Quenching of Cd(5³P₁) by POPOP and sensitization of POPOP by Cd(5³P₁) have been investigated in the vapor phase at total pressures of 10^-1 to 10^-2 torr. Quenching of Cd is observed to occur at a rate of 5.9 X 10^-10 cm³/sec and sensitization of POPOP at a rate of 4.2 X 10^-11 cm³/sec. The sensitized fluorescence rate has been found to be consistent with Forsters long-range dipole-dipole mechanism. Selection of a donor for a possible energy transfer, vapor phase, dye laser is discussed.     

Acetylene spectra with a tunable diode laser: (ν4 + ν5)0+−ν41fQ branches of 12C2H2 and 12C13CH2

The rotational structure of the Q branches of the (ν₄ + ν₅)⁰⁺?ν₄^1f bands of ¹²C₂H₂ and ¹²C¹³CH₂ at 13.7 μm has been observed in a natural sample of acetylene by using a tunable diode laser as a source in a high-resolution infrared grating spectrometer equipped with a precision grating drive. Altogether 23 lines from J = 6 to 28 for ¹²C₂H₂ and 15 lines from J = 6 to 20 for ¹²C¹³CH₂ have been identified. The observed full width at half maximum of the resolved lines of these Q branches is very close to the calculated Doppler width. Molecular constants ν₀ + B″, B′ ? B″ ? 2D″, D′ ? D″, and H′ ? H″ have been derived from the measured line positions of the rotational structure.     

Analytical potential energy function for the electronic states 2^∏1/2 and 2^∏3/2 of O^x2 （x=＋1, -1）

The splitting of potential energy levels for ground state X^2∏g of O^x2 （x = ＋1,-1） under spin-orbit coupling （SOC） has been calculated by using the spin-orbit （SO） multi-configuration quasi-degenerate perturbation theory （SO-MCQDPT）. Their Murrell-Sorbie （M S） potential functions are gained, and then the spectroscopic constants for electronic states 2^∏1/2 and 2^∏3/2 are derived from the M S function. The vertical excitation energies for O^x2 （x = ＋1,-1） are v[O2＋1^（2∏3/2→X^2∏1/2）] =195.652cm^-1, and v[O2^-1（2^∏1/2 →X^2∏3/2）] =182.568cm^-1, respectively. All the spectroscopic data for electronic states 2^∏1/2 and 2^∏3/2 are given for the first time.     

BeH,H2和BeH2的分子结构和势能函数

用二次组态相关(QCISD)和密度泛函(B3LYP)方法, 选用6-311++g(d,p), 6-311++g(3df,3pd)和D95(3df,3pd)基组对H₂, BeH和BeH₂分子的结构进行优化. 得到它们的基态电子态分别为H₂(¹Σ_g), BeH(²Σ)和BeH₂(¹Σ_{g 关键词： BeH 2}')" href="#">BeH₂ 2')" href="#">H₂ 二次组态相关(QCISD) 势能函数     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.     

High-Resolution Stimulated Raman Spectroscopy of Cl2, Cl2, and ClCl

A high-resolution rovibrational Raman spectrum of a sample of Cl₂ has been recorded at room temperature using a quasi-cw stimulated Raman technique. Three Q-branch structures belonging to the fundamental vibrations of the three chlorine isotopomers present in the sample in natural abundances and two weaker Q branches belonging to the first hot bands of the two more abundant isotopomers, ³⁵Cl₂ and ³⁵Cl³⁷Cl, have been observed. Lines with values of J up to 60 for the fundamentals and 50 for the hot bands have been measured in these fully resolved structures. Some additional lines belonging to O and S branches of the fundamentals and hot bands have also been recorded. The analysis of these data has rendered a new and more precise set of rotational molecular constants and band origins for the first three vibrational states of the chlorine isotopomers.     

Charmonium-the 1P1 state

Based on a model which gives agreement with the observed hyperfine and fine splitting of the charmonium states, we predict the mass of ¹p₁ to be 3372 MeV, substantially lower than any previous predicted values. We have also estimated branching ratios and decay rates for the production of this state via channels which become accessible because of its low mass.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.