225∽260 nm波段溴化氰光解动力学系统性研究

本文报道了在自行搭建的时间切片离子速度成像装置上进行的225∽260 nm波段内溴化氰光解动力学的研究. 在该波段内选取了若干溴原子(²P_3/2或²P_1/2)的共振线对产物溴原子的共振电离并采集其切片影像,得到了光解产物的总平动能谱,进而获得了产物氰基的振转态布居等信息. 本文发现了在Br^*通道,产物氰基的内能激发比Br通道低;Br和Br^*通道产物氰基振动的最高布居分别为v=0和1. 另外,还发现对于Br通道,溴化氰分子在长波处与短波处解离时,氰基产物的振转激发差异很大,这揭示了其显著不同的光解动力学.     

离子速度成像技术研究2-溴戊烷的光解离动力学

运用离子速度成像技术研究了2-溴戊烷分子在～234 nm处的光解离动力学. 通过分析光解产物Br(²P_3/2)(简称Br)和Br(²P_1/2) (简称Br*)的速度影像,分别得到其速度分布和角度分布. Br和Br*的速度分布可以用两个高斯分布拟合,分别对应于2-溴戊烷在～234 nm处两个独立的光解离反应通道. 高能的高斯分量对应于C-Br伸缩振动模式的直接解离,低能的高斯分量对应于弯曲振动和C-Br伸缩振动耦合所导致的解离. 确定出光解离产物Br的相对量子产率为0.892,结合Br和Br*碎片的各项异性参数和溴原子的相对量子产率,讨论了³Q₀、³Q₁和¹Q₁激发态分别对产物Br和Br*的贡献. 通过对比溴代戊烷4种同分异构体光解离过程的差异,讨论了分子烷基分支化对光解机理的影响.     

2-溴丁烷在约265 nm光解离的离子速度成像

用离子速度成像结合共振增强多光子电离技术研究了2-溴丁烷分子在264.77和264.86 nm(约265 nm)的光解离动力学．从获得的离子速度图像确定了光解产物Br和Br*碎片的速度分布和角度分布．其速度分布可以由一个窄的高斯分布拟合得到,它对应于沿着C-Br伸缩模式的直接解离．2-溴丁烷在约265nm的光解离中¹Q₁←³Q₀的非绝热跃迁在Br离子碎片的产生中起到非常重要的作用, 确定Br(²P_3/2)的相对量子产额为0.621．通过约265和约234 nm处2-溴丁烷光解的比较发现,各向异性参数和相对量子产率随着波长增加而下降,³Q₀和¹Q₁态势能面交叉几率随着波长增加而降低     

使用时间切片离子速度成像技术研究CF2Cl2光解动力学

本文使用时间切片离子速度成像技术结合共振增强多光子电离技术研究了CF₂Cl₂分子在235 nm附近的光解动力学. 通过测量CF₂Cl₂分子在235 nm附近单光子解离产生的氯原子影像,直接得到了解离产物的速度分布和角分布. 激发态氯原子的速度分布包含高动能组分和低动能组分,分别对应³Q₀电子态的直接解离和由于内转换引起的基态预解离. 基态氯原子的速度分布也包含高动能组分和低动能组分,分别对应³Q₀与¹Q₁电子态的预解离和由于内转换引起的基态预解离. 自由基解离通道被确认,二次解离通道和三体解离通道被排除.     

2-溴丁烷光解离的离子速度成像方法

用离子速度成像结合共振增强多光子电离技术研究了2-溴丁烷在233.62和233.95 nm的光解离动力学. 从离子速度图像确定了光解产物Br和Br*碎片的速度分布和角度分布. Br和Br¤速度分布中包含的两个高斯分量是来自于2-溴丁烷在约234 nm处的两个独立的光解离反应通道. 高能的高斯分量对应于沿着C-Br伸缩模式的直接解离,低能的高斯分量对应于弯曲振动和C?Br伸缩振动耦合形成的排斥模式的解离. 讨论了2-溴丁烷光解离中³Q₀、³Q     

邻碘甲苯分子光解动力学的飞秒时间分辨质谱研究

利用飞秒时间分辨质谱技术研究了邻碘甲苯分子在266 nm激发下的光解动力学. 光解产物碎片通过800 nm强激光场下的多光子电离实现探测. 拟合光解产物C₇H₇自由基和I原子随泵浦-探测延迟时间变化的信号,得到解离时间为38±50 fs,它反映的是266 nm同时激发nσ^*和ππ^*态后C-I键的平均解离时间. 此外,还利用基态碘原子的共振波长298.23 nm作为探测光,通过共振增强多光子电离方法对解离生成的基态碘原子进行了选择性探测. 拟合I⁺随泵浦-探测延迟时间变化的信号,得到解离时间为40±50 fs,这与通过800 nm多光子电离得到的解离时间一致,表明解离生成的主要产物是基态碘原子.     

间氟溴苯分子240 nm紫外光解动力学

The photodissociation dynamics of m-bromofluorobenzene has been experimentally investigated at around 240 nm using the DC-slice velocity map imaging technique. The kinetic energy release spectra and the recoiling angular distributions of fragmented Br(²P_3/2) and Br(²P_1/2) atoms from photodissociation of m-bromofluorobenzene have been measured at different photolysis wavelengths around 240 nm. The experimental results indicate that two dissociation pathways via (pre-)dissociation of the two low-lying ¹ππ^* excited states dominate the production process of the ground state Br(²P_3/2) atoms. Because of the weak spin-orbit coupling effect among the low-lying triplet and singlet states, the spin-orbit excited Br(²P_1/2) atoms are mainly produced via singlet-triplet state coupling in the dissociation step. The similarity between the present results and that recently reported for o-bromofluorobenzene indicates that the substitution position of the fluorine atom does not significantly affect the UV photodissociation dynamics of bromofluorobenzenes.     

Br2+分子离子[1+1]双光子解离动力学

本文利用最近研制的低温离子阱-离子速度成像谱仪在冷离子束中研究了同位素质量分辨的⁷⁹Br₂⁺分子离子的[1+1]双光子激光解离动力学. 借助其1⁴Σ^-_u,3/2态为中间态使⁷⁹Br₂⁺共振吸收两个光子至4∽5 eV区域的高激发态并发生解离. 利用离子速度成像技术获得了光解产物⁷⁹Br⁺的二维速度分布和平动能释放谱. 通过平动能释放谱确定了不同解离能量处量子态分辨的解离产物通道分支比. 光碎片产物的角分布表明⁷⁹Br₂⁺分子离子的双光子解离是1⁴Σ^-_u,3/2态的ΔΩ=0平行跃迁至一个Ω=3/2高解离态发生的. 由于分子激发态中的强自旋-轨道耦合作用,高激发的四重态很可能参与到实验观测的光解过程.     

Cl(2P)+D2→DCl+D反应中波恩-奥本海默近似有效性的交叉分子束研究

本文利用高分辨的里德堡态氘原子标识-交叉分子束装置，研究了碰撞能为4.5∽6.5 kcal/mol范围内Cl(²P)[Cl(²P_3/2)和Cl^*(²P_1/2)]与D₂的反应. 虽然自旋轨道激发态反应Cl^*(²P_1/2)+D₂在波恩-奥本海默(B-O)近似下本应是禁阻的，但实验中观测到了该反应的贡献. 通过测量靠近后向的碰撞能相关的微分散射截面连线，发现低碰撞能下的产物主要来自于B-O近似禁阻的反应Cl^*+D₂. 随着碰撞能的提高，自旋轨道基态反应Cl+D₂的反应性增加明显要比自旋轨道激发态反应Cl^*+D₂更快，并且在高碰撞能下成为产物的主要来源. 实验结果表明：在低碰撞能下，Cl^*中自旋轨道激发态的额外能量，可以帮助B-O近似禁阻的反应Cl^*+D₂越过势垒；然而当碰撞能接近和高于反应势垒时，B-O近似允许的反应Cl+D₂占主导地位. Cl/Cl^*+D₂反应中B-O近似有效性的特征与其同位素反应Cl/Cl^*+H₂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.     

H3PAuPh与(H3PAu)2(1,4-C6H4)2光谱性质的密度泛函研究

用密度泛函(DFT)方法优化了配合物H₃PAuPh(a),(H₃PAu)₂(1,4-C₆H₄)₂(b)的基态的几何结构,并用含时密度泛函方法计算了它们的吸收光谱.结果表明配合物a与 b的最低能量吸收谱线的波长分别为257.5 nm和307.6 nm,皆具有C(2p)→Au(6p)电荷转移参与下的p_π 关键词： 激发态 光谱 密度泛函 3')" href="#">AuPH₃     

Luminescent properties of Dy doped SrMoO4 phosphor

Trivalent dysprosium ions (Dy³⁺) doped strontium molybdate (SrMoO₄) phosphors were synthesized by solid-state reaction and their photoluminescence (PL) properties were investigated. X-ray powder diffraction (XRD) analysis confirmed the formation of SrMoO₄:Dy³⁺. PL measurements indicated that the phosphor exhibited intense emission at 482, 490 (⁴F_9/2→⁶H_15/2) and 575 nm (⁴F_9/2→⁶H_13/2) under UV excitation. The effect of the doping concentration of Dy³⁺in SrMoO₄:Dy³⁺ on the PL was investigated in detail. Na⁺ ion was a good charge compensator for SrMoO₄:Dy³⁺.     

Conductivity and water uptake of Sr4(Sr2Nb2)O11·nH2O and Sr4(Sr2Ta2)O11·nH2O

The hydrated oxygen deficient complex perovskite-related materials Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O were studied at high water vapour pressures over a large temperature range by electrical conductivity measurements, thermogravimetry (TG), and X-ray powder diffraction (XRPD). In humid atmospheres both materials are known to exhibit protonic conductivity below dehydration temperatures, with peak-shaped maxima at about 500 °C. In this work we show that the peaks expand to plateaus of high conductivity from 500 to 700 °C at a water vapour pressure of 1 atm. However, in situ synchrotron XRPD of Sr₄(Sr₂Nb₂)O₁₁·nH₂O as a function of temperature shows that these observations are in fact coincident with melting and dehydration of a secondary phase Sr(OH)₂. The stability of Sr₄(Sr₂Nb₂)O₁₁·nH₂O and Sr₄(Sr₂Ta₂)O₁₁·nH₂O in humid atmospheres is thus insufficient, causing decomposition into perovskites with lower Sr content and SrO/Sr(OH)₂ secondary phases. This, in turn, rationalizes the observation of peaks and plateaus in the conductivity of these materials.     

基质敏化的Er0.1Gd0.9VO4晶体的红外量子剪裁

研究了Er_0.1Gd_0.9VO₄晶体材料的红外量子剪裁现象, 发现了较为有趣的基质敏化的红外量子剪裁现象. 即对于1537.5 nm的⁴I_13/2→⁴I_15/2红外荧光的激发谱存在一个宽而强的337.0 nm波长的激发谱峰,仔细分析可以认定337.0 nm的激发峰对应着基质GdVO₄材料的吸收. 同时,发光谱的测量显示337.0 nm光激发Er_0.1Gd_0.9VO₄材料的基质吸收带时导致的1537.5 nm⁴I_13/2→⁴I_15/2红外荧光的积分强度比其他所有荧光的积分强度的总和大了接近10倍, 它的红外量子剪裁效率仅次于最强的²H_11/2能级受激的红外量子剪裁效率且比其他能级都强. 关键词： 红外的量子剪裁 太阳能电池 0.1Gd_0.9VO₄晶体材料')" href="#">Er_0.1Gd_0.9VO₄晶体材料     

Ab initio study of phase stability,thermodynamic and elastic properties of C3N2 derived from cubic C20

In this work, we report a quite different conclusion from Tian et al. [Phys. Rev. B 78 (2008) 235431]. It is proved that β-C₃N₂ is the only phase under high pressure, and α-C₃N₂ does not exist. β-C₃N₂ is a covalent crystal composed of strong CC and CN covalent bonds. Band gap of β-C₃N₂ increases with pressure. The width of antibonding state, shown in partial density of states (PDOS), keeps about 5 eV with rising pressures, which brings stable CN or CC covalent bonds. At sufficiently low temperatures, heat capacity (C_v) is proportional to T³; and at intermediate temperatures, C_v is governed by the details of vibrations of the atoms; finally, C_v reaches to β-C₃N₂'s Dulong–Pettit limit (about 120 J/mol K). Though thermal expansion coefficient (α) increases with temperature, α is less than 1×10⁻⁵ K⁻¹. Elastic constants rise with pressure, but shear moduli is quite steady which increases just a little with pressures.     

NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Four ⁸¹Br NQR lines in 4-NH₂C₅H₄NHBiBr₄·H₂O were observed in the temperature range between 77 and ca. 380 K; with increasing temperatures the respective sets of higher and lower two resonance lines coalesced into single lines discontinuously at 274 K, showing the occurrence of a first-order type phase transition of this crystal. The transition was confirmed with heat anomaly on a DTA curve. Each higher and lower line of high-temperature phase is assignable to the terminal Br atoms and the bridging ones of one-dimensional poly anions (BiBr₄ ⁻) _n in the crystal structure (C2/c), which was investigated by a X-ray structure analysis at room temperature. The 1/T ₁ temperature dependence of ⁸¹Br NQR follows the usual T ² law in the temperature range between 77 and ca. 140 K, being explained by fluctuation of the EFG at Br nucleus due to lattice vibrations. The T ₁ vs. 1/T curve in the temperature range between about 160 and 190 K was describable by the exponential curves, allowing us the estimation of activation energies. These exponential behaviors of T ₁ of ⁸¹Br NQR are attributable to the fluctuations caused by the thermal motion of 4-NH₂C₅H₄H⁺ ions. Echo signals of the ⁸¹Br NQR could not be detected above 190 K owing to poor S/N with very short T ₂.     

Synthesis and Sm/Sm doping effects on photoluminescence properties of Sr4Al14O25

Complete and partial samarium reduction was achieved under strong reducing atmosphere by solid-state and combustion synthesis of Sr_3.96Sm_0.04Al₁₄O₂₅. Dependence of different fluxing agents on the formation of various strontium aluminates was examined. The samples were investigated by X-ray powder diffraction, temperature dependent luminescence decay and photoluminescence measurements. Excitation with UV radiation resulted in sharp and well resolved emission lines of samarium ions. Distinct temperature behavior for Sm²⁺ and Sm³⁺ were detected in the range of 100-500 K. Estimated emission thermal quenching values (TQ_1/2) for divalent samarium were approximately 270 K while for trivalent state around 660 K. Measured luminescence decay values of Sm²⁺ are substantially lower than for Sm³⁺,≈1.7 and ≈2.7 ms, respectively. The spectral feature of Sm²⁺ emission spectrum indicates that dopant occupies low symmetry site in Sr₄Al₁₄O₂₅ compound.     

氢同位素氚水T2O(X1A1)的解析势能函数

获得T₂O(X¹A₁)解析势能函数的主要困难在于Born-Oppenheimer近似下T₂O(X¹A₁)与H₂O(X¹A₁)势能函数的不可区分性.然而,在Born-Oppenheimer近似下,分子势能函数实际上是键长、键角这些 关键词： 2O(X¹A₁)')" href="#">T₂O(X¹A₁) 同位素效应 解析势能函数     

Mo掺杂SrBi4Ti4O15陶瓷的铁电介电性能

用传统的固相烧结工艺，制备了钼掺杂铁电陶瓷样品SrBi₄Ti₄O₁₅(SBTi)铁电陶瓷SrBi_4-2x/3Ti_4-xMo_xO₁₅(x=0.00，0.003，0.012，0.03，0.06，0.09).X射线衍射的结果表明，样品均为单一的层状钙钛矿结构相，Mo掺杂未改变SBTi的晶体结构.通过扫描电子显微镜观测发现，样品晶粒为片状，随掺杂量的增加，晶粒逐 关键词： 4Ti₄O₁₅')" href="#">SrBi₄Ti₄O₁₅ Mo掺杂 剩余极化 居里温度     

La掺杂SrBi4Ti4O15铁电材料性能研究

按x=0.00，0.10，0.25，0.50，0.75和1.00，采用固相烧结工艺，制备了不同La掺杂量的SrBi_4-xLa_xTi₄O₁₅的陶瓷样品. 用x射线衍射对其微结构进行了分析，并测量了铁电、介电性能.结果发现，La掺杂未改变SrBi₄Ti ₄O₁₅的晶体结构.随掺杂量的增加，样品的矫顽场(E_c)下降，剩余极化(2P_{关键词： 4-x}La_xTi₄O₁₅')" href="#">SrBi_4-xLa_xTi₄O₁₅ La掺杂 铁电性能 相变温度 弛豫铁电