β-Na(Y1.5Na0.5)F6:Tm—A blue upconversion phosphor

A luminescent material β-Na(Y_1.5Na_0.5)F₆ doped with Tm³⁺ was synthesized by a solid-state reaction method for a steady phosphor of blue upconversion. Under the 671 nm laser excitation, the green emission band of 511 nm due to the ¹D₂→³H₅ transition is obtained for the first time, while the ultraviolet emission band is also observed at 368 nm, associated with the ¹D₂→³H₆ transition. Especially, a wide band of blue emissions is obtained at the wavelength region of 440-490 nm, originated mainly from the ¹D₂→³F₄ (450 nm) and ¹G₄→³H₆ (471-487 nm) transitions, which have potential application in tunable solid-state blue laser of Tm³⁺. The upconversion mechanism is explored in terms of the energy-level structures of Tm³⁺ ion and the power dependence of upconverted emission intensity, which is believed to be performed by excited-state absorption.     

Role of hydrogen bonding on the spectroscopic properties of thiazolidinedione derivatives in homogeneous solvents

In this work, three newly synthesized derivatives of thiazolidinediones, with potential for application as drugs in pharmaceutical industry and free radical scavenging activity, have been taken up to investigate their behaviour in different homogeneous solvents. The purpose of this work is to study the solvation characteristics in ground and excited states of the derivatives by monitoring the absorbance and fluorescence band maxima. The steady state and time resolved fluorescence studies in protic and aprotic solvents have been rationalized on the basis of solute–solvent interaction and substituent effect on these photophysical processes have been analyzed. Substituents at different positions of the aryl moiety affect the hydrogen bond formation ability of the probes.     

Reactions of small negative ions with O2(a Δg) and O2(X Σg)

The rate constants and product ion branching ratios were measured for the reactions of various small negative ions with O₂(X ³Σ_g⁻) and O₂(a ¹Δ_g) in a selected ion flow tube (SIFT). Only NH₂⁻ and CH₃O⁻ were found to react with O₂(X) and both reactions were slow. CH₃O⁻ reacted by hydride transfer, both with and without electron detachment. NH₂⁻ formed both OH⁻, as observed previously, and O₂⁻, the latter via endothermic charge transfer. A temperature study revealed a negative temperature dependence for the former channel and Arrhenius behavior for the endothermic channel, resulting in an overall rate constant with a minimum at 500 K. SF₆⁻, SF₄⁻, SO₃⁻ and CO₃⁻ were found to react with O₂(a ¹Δ_g) with rate constants less than 10⁻¹¹ cm³ s⁻¹. NH₂⁻ reacted rapidly with O₂(a ¹Δ_g) by charge transfer. The reactions of HO₂⁻ and SO₂⁻ proceeded moderately with competition between Penning detachment and charge transfer. SO₂⁻ produced a SO₄⁻ cluster product in 2% of reactions and HO₂⁻ produced O₃⁻ in 13% of the reactions. CH₃O⁻ proceeded essentially at the collision rate by hydride transfer, again both with and without electron detachment. These results show that charge transfer to O₂(a ¹Δ_g) occurs readily if the there are no restrictions on the ion beyond the reaction thermodynamics. The SO₂⁻ and HO₂⁻ reactions with O₂(a) are the only known reactions involving Penning detachment besides the reaction with O₂⁻ studied previously [R.S. Berry, Phys. Chem. Chem. Phys., 7 (2005) 289–290].     

一类效应代数的态表示定理

1994年, Foulis和Bennett在表示不可精确测量的量子逻辑结构时引入了效应代数. 该文用直接构造的方法, 给出一类效应代数上的态表示定理. 即, 若Ω是紧的 Hausdorff 拓扑空间, 令E(Ω)={f: f∈C(Ω), 0≤f≤1}, 则φ 是(E(Ω),Ο, 0, 1) 上的态当且仅当Ω 上存在唯一的正则Borel 概率测度μ使得对每个f (E(Ω),Ο, 0, 1),φ (f)=∫_Ω f dμ.     

3-二甲氨基-2-甲基丙烯醛S2激发态结构动力学

采用共振拉曼光谱和完全活性自洽场理论计算研究了3-二甲氨基-2-甲基丙烯醛（DMAMP）光激发到S2（ππ^＊）态后的光物理性能,在B3LYP／6—311＋＋G（d,p）水平计算确定了DMAMP与其三种异构体之间的基态异构化能垒,指认了振动光谱．采用涵盖紫外强吸收带的激光波长,获得了DMAMP在环己烷、乙腈和甲醇溶剂中的A-带共振拉曼光谱,含时密度泛函方法计算确定了该光谱中基频的相对强度,发现振动-电子耦合发生在S2（）态的Franck—Condon区域．CASSCF计算方法确定低单重和三重激发态、势能面锥形交叉点和系间窜跃点的激发能．共振拉曼光谱强度模式分析和CASSCF计算获得了DMAMP的A一带短时结构动力学和其后的衰变动力学表明,C1=06和C2=C3之间的瞬时去共轭效应发生在S2（ππ^＊）态的Franck—Condon区域,激发态电荷重分布机制表明,C3和二甲氨基之间以及C1和C2之间的共轭增强效应发生在波包离开Franck-Condon区域后．C1=06和C2=C3之间的去共轭效应使得-C3=N（CH3）2沿着C2-C3键旋转更加容易,C1-C2之间以及C3和N（CH3）的共轭增强效应使得绕C1-C2和C3-N5旋转变得比较困难．这些表明DMAMP初始结构动力学沿着CI-1（S2／S0）交叉点展开,而沿CI-2（S2／S0）和[CI-3（S2／S0）交叉点展开的几率可以忽略,提出了DMAMP分子受光激发从S2,FC（ππ^＊）经由各锥形交叉点和各系间窜跃点回到S0或T1,min的两个衰变通道。     

间-吡啶基紫外光化学中的氢原子解离通道

利用高里德堡态氢原子飞行时间探测技术, 在224～248 nm激发波长研究了间-吡啶基紫外光化学中的氢原子解离通道的动力学过程．氢原子光解碎片产率谱显示在234 nm附近有较宽的吸收．产物的平动能释放较小;在224～248 nm激发波长区间平均〈 fT〉是0.12～0.19．产物的平动能分布显示产物是H＋HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶,以H HC≡C-CH=CH-C≡N为主要的氢原子生成通道．氢原子碎片具有各向同性的角度分布．研究结果表明,在紫外电子态激发以后,间-吡啶基经过内转换到电子基态,再经由单分子解离到H HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶产物．间-吡啶基的紫外光解机理和以前报道过的邻-吡啶基的紫外光解机理相似．     

2-乙酰基-1-甲基吡咯激发态结构动力学及溶剂效应的共振拉曼光谱和密度泛函理论计算

获取了覆盖紫外光谱中A带和B带吸收的共7个不同激发波长的共振拉曼光谱, 并结合密度泛函理论方法研究了2-乙酰基-1-甲基吡咯(2-Ac-NMP)的A带和B带电子激发和Franck-Condon区域结构动力学. 在TD-B3LYP/6-311++G(d,p)计算水平上, A带和B带吸收的跃迁主体为π→π^* . A带和B带共振拉曼光谱分别指认为13个振动模式和8个振动模式的基频、泛频和组合频, 其中C＝O伸缩振动(ν₈)、C3-C4-C5不对称伸缩振动+C2-C6伸缩振动(ν₁₄)及环上CH面内摇摆(ν₁₈)对拉曼光谱强度贡献最大, 表明2-Ac-NMP的S_π激发态结构动力学主要沿反应坐标展开. 考察了溶剂对共振拉曼光谱强度模式的影响, 结果表明, 在同一溶剂中, 随激发波长由长变短, C＝O伸缩振动模(ν₈)的强度呈现出由强变弱再变强的现象. 这种变化规律与Franck-Condon区域S_n/S_π态混合或势能面交叉相关, 并受溶剂的有效调控.     

双脉冲注入式LD模块的红外能级寿命可见区测试系统

Er3+的4I_13/2能级寿命的长短对评估Er3+掺杂材料在光通讯波段的应用十分重要。基于980 nm双脉冲注入式LD激发下的Er3+激发态吸收上转换发光,测量在不同双脉冲时间间隔下的上转换红光发光强度,再根据上转换红光的发光强度随双脉冲时间间隔的变化关系,推导出了Er3+红外4I_13/2能级寿命的拟合公式,实现了红外能级寿命的可见区测量。因此,结合兼具时间间隔可调和同步脉冲取样的双脉冲注入式LD模块和光电倍增管(R2658),就可以实现所有Er3+红外能级寿命的测量,这是一种十分经济的微秒量级荧光寿命测试系统。     

大气压下氩原子谱线辐射诊断试验研究

大气压下介质阻挡放电应用领域具有多范畴、深广度、常态化等优势,针对同轴电极放电试验进行了系列参数诊断。采用自主研发的介质阻挡放电助燃激励器,在一个标准大气压、放电频率11.4 kHz、放电峰值电压5.4～13.4 kV(间隔1.0 kV)条件下进行了氩气电离试验。采用原子发射光谱法(AES)对氩等离子体谱线的激发、分光进行了检测分析;选用二谱线法及Boltzmann法测试了电子激励温度;根据Stark展宽效应计算了电子密度;获得了电子激励温度及电子密度随放电峰值电压增长的变化规律。结果表明,在试验电压条件下电子激励温度并不随外加电压的升高而递增,这表明通道内微放电的主要特征并不依赖于外部电压的供给,而是取决于气体组份、气体压强和放电模型,增大外加放电电压仅增加单位时间内微放电的数量,经整合电子激励温度可达3 500 K符合典型的低温等离子体特征;电子密度随外加电压的增长而趋于准线性趋势,电子密度数量级可达到108～109 cm-3,电离度偏弱。这些参数的探索对等离子体研讨有重大意义。     

直流激励的大气压氩气喷枪的光谱研究

利用正高压驱动空心针-板喷枪装置,通入工作气体氩气,在大气压空气中产生了均匀稳定的喇叭状等离子体羽。电学和光学测量结果表明,放电虽然是在直流电源驱动下工作,但放电为周期性的脉冲。通过对等离子体羽发光信号进行空间分辨测量,研究了脉冲的形成机理,发现除针尖附近的电晕放电外,等离子体羽是以正流光(等离子体子弹)从针尖向着接地电极方向传播的。采用光谱学方法,对电子激发温度随电压的变化及其空间分布进行了测量。结果表明,电子激发温度(约为3 eV)随电压的增大而升高,在一定电压下,电子激发温度沿气流方向也在升高。