Laser activity at 1.18, 1.07, and 0.97 microm in the low-phonon-energy hosts KPb2Br5 and RbPb2Br5 doped with Nd3+

For the first time to the authors' knowledge, laser activity has been achieved in low-phonon-energy, moisture-resistant bromide host crystals, neodymium-doped potassium lead bromide (Nd3+:KPb2Br5) and rubidium lead bromide (Nd3+:RbPb2Br5; RPB). Laser activity at 1.07 microm was observed for both crystalline materials. Laser operation at the new wavelengths 1.18 and 0.97 microm that resulted from the 4F5/2 + 2H9/2 - 4IJ transitions (J=13/2 and J=11/2) in Nd:RPB was achieved in a solid-state laser material. Rare-earth-doped MPb2Br5 (M=K, Rb) is a promising candidate for long-wavelength infrared applications because of its low phonon frequencies and other favorable features. In principle, Nd3+:MPb2Br5 has high potential for laser operation at new wavelengths as well as for the achievement of short-wavelength lasing as a result of upconversion.     

丁酮分子的多光子电离-离解机理

研究了丁酮分子经(n0,3d)共振的多光子电离-离解机理(MPID).多光子电离-飞行时间质谱测得的主要离子产物是C2H3O+和CH3CH+2,C2H3O+的强度为CH3CH+2的2～5倍,还有少量C2H+2,C2H+3和CH+3离子,未见到母体离子.主要离子产物的分质量多光了电离谱结构相似,而各离子产物的光强指数不同.实验结果说明丁酮分子的多光子电离-离解机理符合母体离子阶梯模型,文中用梯开关模型对主要产物离子的产生机理进行了解释.     

甲醇/水混合团簇的多光子电离质谱研究

利用多光子电离技术结合飞行时间质谱仪对甲醇/水混合团簇进行了研究.在脉冲激光波长为355 nm条件下观测到团簇离子.主要的电离产物为质子化的(CH3OH)n(H2O)H+(n=l-13)混合团簇离子与(CH3OH)nH+团簇离子,经分析(CH3OH)1o(H2O) H+和(CH3OH)3H+为幻数结构.甲醇水混合团簇电离后团簇离子发生内部质子化转移反应是形成质子化团簇离子的主要原因.不同尺寸团簇离子信号强度随电离激光光强变化的光强指数曲线显示,团簇均发生四光子电离过程.     

用密度泛函方法研究质子化苯基丙酮-水团簇

应用密度泛函B3LYP/631+G(d,p)计算方法,对质子化苯基丙酮水团簇这个弱相互作用体系进行了全自由度能量梯度优化,得到该系列团簇的稳定结构.结果表明,H+C8H8OH2O团簇的形成过程为一无能垒的反应过程,在质子与C8H8O分子中O原子的距离为1.015时达到平衡几何.对H+C8H8O(H2O)n(n=1,2,3)团簇,质子位于C8H8O分子和水分子之间,且随着团簇尺寸的增加,质子与C8H8O分子中O原子之间的距离也增加;C8H8OH+H2O可以视为溶剂壳.而对H+C8H8O(H2O)n(n=4,5,6,7,8)团簇,质子位于两个水分子之间,形成H5O2+结构,即C8H8OH5O2+为该系列团簇的中心结构,新增加的水分子以从不同方向进攻这个中心的方式形成更大尺寸的团簇.     

Symmetry-resolved absorption spectra of vibrationally excited CO2 molecules

Symmetry-resolved x-ray absorption spectroscopy has been first carried out on high-temperature molecules. From the angle-resolved ion yield spectra of CO2 both at room temperature and at 430 degrees C, symmetry-resolved absorption profiles of the C 1s(-1) 2pi(u) and O 1s(-1) 2pi(u) resonances have been extracted for the vibrational ground state molecules and bending-vibration excited ones. The profiles change dramatically between them, and the Renner-Teller effect becomes more evident for the vibrationally excited molecules. The effects of the multimode vibronic coupling are suggested for the O 1s(-1) 2pi(u) and O 1s(-1) 3s sigma(g) resonances.     

碘-四氯化碳萃取光度法间接测定痕量草酸根

本研究了在稀硫酸介质中，一定的反应条件下，碘酸根与草酸根反应，稀释出 一定量的碘，据此建立了碘－四氯化碳萃取光度法间接测定草根的方法。反应温度控制在９０℃，反应时间控制在３ｍｉｎ，反应酸度控制在ｐＨ１．０￣２．０，共顾离子基本不干扰测定，草酸根的最低检测限为０．０８μｇ／ｍＬ，通过方法的回收率试验以及与其他测定方法进行比较得到了满意的结果，回收率在９６￣９８％之间。     

激光烧蚀Al热原子与CF4反应中C2的形成及其发光光谱研究

脉冲激光烧蚀金属平面铝靶产生的热原子与气相CF4碰撞反应中，在400—600nm之间观测到激发态C2分子的发光光谱，它们可归属为Swan带的d3Πg-a3Πu跃迁中Δv＝２，1，0，-1，-2五个振动序列（v'≤6）.光谱强度分析表明，C2激发态的振动温度达6340K左右.与激光烧蚀Al＋O2反应生成AlO的实验结果以及激光烧蚀Cu＋CF4的光谱比较，对比Al(2P1/2-2S1/2,3944nm）和C2的d—a跃迁（0—0）带带头（5165nm)的飞行时间轮廓，认为激发态的Al(2S1/2)原子通过 关键词： 激光烧蚀 发光光谱 C2分子     

Far-Infrared Laser Magnetic Resonance Spectroscopic Study of the nu(2) Bending Fundamental of the CCN Radical in Its &Xtilde;(2)Pi(r) State

Bending vibration-rotation transitions between the (010) μ(2)Sigma(-) and (000) (2)Pi(r) vibronic states of the CCN radical in its ground electronic state have been observed using far-infrared laser magnetic resonance (FIR LMR) spectroscopy. Thirteen FIR laser lines were used to record 769 resonances. The LMR data, combined with previous data, were used to determine vibrational, Renner-Teller, fine-structure, rotational, hyperfine, and molecular g-factor parameters using a least-squares fitting routine. The model used was an N(2) effective Hamiltonian modified to include the Renner-Teller effect explicitly in a (2)Pi electronic state. The band origin for the (010) μ(2)Sigma(-) <-- (000) &Xtilde;(2)Pi(r) transition was determined to be 179.598176 +/- 0.000067 cm(-1). The spin-orbit splitting in the ground state was refined and the complete set of (14)N-hyperfine parameters determined for the first time.     

Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry

Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m?=?1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n?=?2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m?=?1-12), P(n)(+) (n?=?2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n?=?1, 2-88 (even numbers)), Au(2)P(n)(+) (n?=?1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n?=?1-6, 8, 9, 14), Au(4)P(n)(+) (n?=?1-9, 14-16), Au(5)P(n)(+) (n?=?1-6, 14, 16), Au(6)P(n)(+) (n?=?1-6), Au(7)P(n)(+) (n?=?1-7), Au(8)P(n)(+) (n?=?1-6, 8), Au(9)P(n)(+) (n?=?1-10), Au(10)P(n)(+) (n?=?1-8, 15), Au(11)P(n)(+) (n?=?1-6), and Au(12)P(n)(+) (n?=?1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m?=?1-5), P(n)(-) (n?=?2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n?=?4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n?=?2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n?=?6-11, 32), Au(4)P(n)(-) (n?=?1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n?=?1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of new Au-P materials with specific properties.     

Enhancing high-order above-threshold dissociation of H2+ beams with few-cycle laser pulses

High-order (three-photon or more) above-threshold dissociation (ATD) of H(2)(+) has generally not been observed using 800 nm light. We demonstrate a strong enhancement of its probability using intense 7 fs laser pulses interacting with beams of H(2)(+), HD(+), and D(2)(+) ions. The mechanism invokes a dynamic control of the dissociation pathway. These measurements are supported by theory that additionally reveals, for the first time, an unexpectedly large contribution to ATD from highly excited electronic states.     

钒氧化物团簇正离子与乙烯在流动管反应器中的反应

利用一套自建的配有团簇产生和化学反应源的飞行时间质谱装置，研究了钒氧化物团簇正离子(VmOn+)与乙烯(C2H4)在气相条件下的反应．激光溅射产生的钒等离子体与氧气分子在超声喷射下反应，产生m=1?10和n=1?26 (具体数字依赖于m) 的VmOn+，然后与流动管反应器中的乙烯反应． 该实验条件下， 氧饱和团簇(2n?5m)往往含有氢原子(VmOnH2x+)．与乙烯反应时，相对于VmOnH2x+，VmOn+表现出比较高的反应活性，而且，小团簇比大团簇具有较高的反应活性．观测到的反应产物大都为碰撞结合体V     

RbH(X1∑+,v=O～2)能级与H2碰撞振动能量转移

利用积分时间分辨荧光光谱方法,研究了RbH(X1∑+,v=0～2)与H2间的振动碰撞能量转移.在Rb-H2混合样品池中,泵浦激光双光子激发Rb原子至6D态,Rb(6D)与H2反应生成RbH(x1∑+)分子,探测激光延迟泵浦激光20 ns,通过激光感应荧光光谱(LIF)的测量,确定了X1∑+(v=0～2,J)原生态的转动...     

苯基羧甲基亚砜体系中高氯酸铥对高氯酸铽的荧光增强效应研究

合成了不同摩尔比的苯基羧甲基亚砜高氯酸铽、铥异核配合物 ,对配合物进行了组成分析 ,确定了配合物组成为 (Tb1 -xTmx) L2 (ClO4 ) ·2H2 O(x=0 0 0 0～ 0 2 0 0 ,L=C6 H5SOCH2 COO- )。通过IR光谱及摩尔电导的测定推测了配位情况 ,溶解性实验表明配合物在乙醇、丙酮等极性溶剂中具有很高的溶解性。荧光光谱实验表明 :当 x =0 0 0 1～ 0 10 0时铥对铽的荧光均产生敏化增强效应 ,当x =0 0 0 1时敏化强度最大 ,可使Tb3+ 荧光强度增加 32 6 %。     

QED effects in molecules: test on rotational quantum states of H2

Quantum electrodynamic effects have been systematically tested in the progression of rotational quantum states in the X?1Σ(g)(+), v=0 vibronic ground state of molecular hydrogen. High-precision Doppler-free spectroscopy of the EF?1Σ(g)(+)-X?1Σ(g)(+) (0,0) band was performed with 0.005 cm(-1) accuracy on rotationally hot H2 (with rotational quantum states J up to 16). QED and relativistic contributions to rotational level energies as high as 0.13 cm(-1) are extracted, and are in perfect agreement with recent calculations of QED and high-order relativistic effects for the H2 ground state.     

High-Resolution Laser Photoacoustic Spectroscopy of HSiF(3): The 5nu(1) and 6nu(1) Overtone Bands

A spectrum of HSiF(3) has been recorded at room temperature with a gas pressure of 20-50 Torr in the near-infrared region. A laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a titanium:sapphire ring laser was employed. The 5nu(1) and 6nu(1) overtone bands of H(28)SiF(3) associated with the Si-H stretching have been observed at high resolution (3 x 10(-2) cm(-1)) in the regions 10 900-10 960 and 12 875-12 925 cm(-1), respectively. About 450 lines of the 5nu(1)-0 band have been assigned (J 相似文献   

Charge and substituent effects on the stability of porphyrin/G-quadruplex adducts

The adduct ions of two tetramolecular G-quadruplexes formed from the d(TGGGGT) and d(TTGGGGGT) single strands with a group of cationic porphyrins, with different charges and substituents, and one neutral porphyrin, were investigated by ESI-MS and ESI-MS/MS in the negative ion mode. Formation of [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions (where Q = quadruplex, n = number of quartets minus 1, P = porphyrin and p(+) = 0,1,2,3,4) indicates that the porphyrins are bound outside the quadruplexes providing an additional stabilization to those structures. The fragmentation pathways of the [Q + nNH(4)(+)+P(p+)-(z + n + p)H(+)](z-) adduct ions depend on the number of positive charges (p(+)) of the porphyrins and on the overall complex charge (z(-)), but do not show a significant dependence on the type of the substituent groups in the porphyrins. Formation of the 'unfilled' ions [Q + P(p+)-(z + p)H(+)](z-) predominates for porphyrins with a higher number of positive charges. Strand separation with the formation of [T + P(p+)-(z-2 + p)H(+)]((z-2)-) and (SS-2H(+))(2-) ions, where T = [d(TG(4)T)](3) and [d(T(2)G(5)T)](3) and SS = d(TG(4)T) and d(T(2)G(5)T) is only observed for the complexes with a higher overall negative charge. Porphyrin loss with the formation of [Q + nNH(4)(+)-(z + n)H(+)](z-) ions occurs predominantly for the neutral and monocharged porphyrins. The predominant formation of the 'unfilled' ions, [Q + P(p+)-(z + n)H(+)](z-), for porphyrins with a higher number of charges shows that these porphyrins can prevent strand separation and preserve, at least partially, the quadruplex structure.     

高激发振动态RbH（Х1Σ+,ν″=15～22）与H2,N2的振动-振动碰撞能量转移

脉冲激光激发Rb原子至6 D态,Rb(6 D)与H2反应生成RbH(Х1Σ+,ν″=0～2)振动态。研究了RbH(Х1Σ+)高位振动态与H2,N2间的碰撞弛豫过程,利用泛频泵浦分别激发Х1Σ+(ν″=0)至Х1Σ+(ν″=15～22)各振动态,检测激光激发Х1Σ+(ν″)至A1Σ+(ν′),测量A1Σ+(ν′)的时间分辨激光感应荧光光谱,利用Stern-Volmer方程,得到振动能级ν″的总的弛豫速率系数kν(H2)。在H2和N2的混合气体中,总弛豫速率系数kν(H2+N2)与α(H2的摩尔配比)成直线的关系,其斜率为kν(H2)-kν(N2),而截距为kν(N2)。对于ν″<18主要发生单量子弛豫(Δν=1)过程,kν(H2)和kν(N2)与振动量子数ν″均成线性增加关系。对于ν″≥18,多量子弛豫(Δν≥2)过程及共振振动-振动转移起重要作用。对于RbH(ν″=21)+N2(0),测量ν″=16的布居数时间演化轮廓,在20μs内有一个锐锋,在100～200μs内有一个较低的宽峰,锐锋相应于RbH(ν″=21)+N2(0)→RbH(ν″=16)+N2(1)的共振转移过程,而宽峰是由相继的单量子过程产生的。     

Fourier Transform Spectra of the E(2)Pi(u)-X(2)Pi(g)((3/2)) System of CuCl(2)

High-resolution Fourier transform spectra of the laser-induced fluorescence of (63)Cu(37)Cl(2) produced in a cell have been recorded following excitation of a single vibronic level of the E(2)Pi(u) electronic state. Fluorescence occurs in combination bands to a broad spread of levels in the ground electronic state. A global vibronic model is proposed for the ground state based on an effective Hamiltonian, which fits the experimental data (2782 fluorescence lines, lower state quantum numbers: v(1) = 0-6, v(2) = 0-2, v(3) = 0-6, and J = 4(1/2)-80(1/2)) to 0.019 cm(-1) rms error. Vibrational, rotational and Renner-Teller parameters are obtained (e.g., omega(2) = 95.195(36) cm(-1), B(e) = 0.055106(3) cm(-1), epsilon = -0.1893(28)). A revised value for the equilibrium internuclear distance Cu-Cl is deduced: r(e)(Cu-Cl) = 0.20341(3) nm. The energy diagram of vibronic levels in the ground state is plotted up to 4000 cm(-1). Copyright 2000 Academic Press.     

苯酚-水团簇C_6H_5OH(H_2O)_n(n=1-6)结构与电子性质的密度泛函理论研究

利用密度泛函理论,在B3LYP/6-31+G(d, p)基组水平上对苯酚-水团簇C_6H_5OH(H_2O)_n(n=1-6)的可能构型进行全优化,得到了团簇的稳定结构;在B3LYP/6-311++G(d, p)基组水平上计算得到了各团簇构型的总能量和结合能,结果显示,在团簇尺寸较小(n≤5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为平面的环状结构,团簇尺寸较大(n5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为三维立体结构.通过对团簇结合能的二阶差分、最高占据轨道与最低空轨道之间的能隙、费米能级和电离能的分析发现,团簇C_6H_5OH(H_2O)_2的最低能量结构具有较高的稳定性,可能具有幻数结构.     

利用CARS技术研究激发态Rb2和H2的碰撞转移

利用相干反斯托克斯拉曼光谱(coherent anti-stokes Raman spectroscopy,CARS)探测技术,研究了激发态Rb2与H<,2>间的电子-振转能级的碰撞转移.扫描CARS谱确认了H<,2>分子仅在v=1,J=1,2及v=2,J=0,1,2能级上有布居,用n1,n2,n3,n4,n5分别表示...