乙二醇溶液中直管圆锥泡声致发光光脉冲和光谱

在U型管声致发光装置的基础上建立了一套新型的声致发光装置—直管圆锥泡声致发光装置,详细地介绍了此装置的结构和实验操作步骤,利用此装置得到了超强的发光脉冲。测量得到了乙二醇溶液中圆锥泡声致发光的发光脉冲,结果显示脉冲半宽度大约为80 μs左右,远远高于其他声致发光形式所产生的脉冲宽度,这主要是由于圆锥泡可以获得远远高于超声声致发光中气泡所能得到的能量。发光光谱为一从紫外光至可见光波长范围的连续谱,上面叠加C₂有d3Π_g→d3Π_u的跃迁形成的五个序列谱带,分别对应于Δν＝-2,Δν＝-1,Δν＝0,Δν＝1和Δν＝2;同时叠加有CN的B2Σ+→X 2Σ+跃迁形成的3个序列谱带和CH的A2Δ→X 2Π 跃迁谱带。特别是实验中测量得到了斯旺带光谱序列谱带清晰的振动结构。最后,通过与理论模拟得到的斯旺带光谱相对强度的比较,估算得到了C₂分子的振动温度大约为(4 200±200) K。     

SH（D）和OH（D）自由基基态的结构与势能函数

采用QCISD（T）/ 6-311++G（3df,2pd） 和QCISD/6-311++G（3df,2pd）方法计算优化了SH（D）和OH（D）自由基分子基态X²Π的分子结构和离解能.并采用最小二乘法拟合Murrell-Sorbie 函数得到了相应的势能函数,由此计算的振转常数与实验光谱数据符合得相当好. 关键词： SH和OH自由基分子 X²Π）')" href="#">基态（X²Π） Murrell - Sorbie函数 势能函数     

PS自由基X2Π态的势能曲线和光谱性质

采用Davidson修正的内收缩多参考组态相互作用方法(icMRCI+Q) 结合Dunning等的相关一致基计算了PS自由基X²Π 态势能曲线. 利用三阶Douglas-Kroll Hamilton近似结合cc-pV5Z相对论收缩基进行了相对论修正计算. 利用aug-cc-pCV5Z基组对势能曲线进行了核价相关修正计算, 并将总能量外推至完全基组极限. 拟合得到了X²Π态的主要光谱常数R_e, ω_e, ω_ex_e, ω_ey_e, B_e, α_e 和D_e, 与实验结果符合较好. 利用Breit-Pauli算符, 研究了旋轨耦合效应对势能曲线的影响, 得到了两条Ω 态的势能曲线. 详细分析了在旋轨耦合计算中, 核电子相关与冻结核近似对电子结构和光谱性质的影响. 在icMRCI+Q/56+DK+CV+SO理论水平上得到了两个Ω 态的主要光谱常数T_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e 和α_e, 结果与实验结果一致. 在平衡位置处, 本文的X²Π态旋轨耦合能量分裂值为 323.73 cm^-1, 与实验结果321.93 cm^-1较为一致. 通过求解双原子分子核运动的径向Schrödinger方程, 找到了无转动PS自由基X²Π态及其两个Ω 态的全部振动态, 还分别计算了它们相应的振动能级和惯性转动常数等分子常数, 这些结果与已有的实验值一致. 关键词： 势能曲线 光谱常数 分子常数 旋轨耦合     

基态S和D原子的低能弹性碰撞及SD(X2Π)自由基的准确相互作用势与分子常数

使用Gaussian03程序包提供的CCSD（T）理论及Duning等的相关一致基cc-pVnZ和aug-cc-pVnZ （n=2, 3, 4, 5）, 对SD（X²Π）自由基的平衡核间距、谐振频率及相互作用势进行了计算, 并拟合出了相应的光谱常数. 在CCSD（T）/aug-cc-pV5Z理论水平下, 光谱常数D₀, D_e, R 关键词： 弹性碰撞 总截面 光谱常数 分子常数     

稀土盐水溶液单泡声致发光中的特征光谱

在溶有稀有气体的稀土盐氯化铽水溶液中进行了单泡声致发光光谱的研究. 在固定驱动超声频率、不同驱动声压下, 观察到了一系列OH自由基从第一激发态A²∑⁺到基态X²Π 各振动能级跃迁所产生的谱线, 包括波长307 nm处的(0, 0)跃迁谱线, 335 nm处的(0, 1)跃迁谱线以及276 nm处的(1, 0) 跃迁谱线等. 实验结果表明较高的驱动声压有利于 276 nm处谱线的产生, 而较低的驱动声压则有利于 307 与 335 nm 处谱线的产生. 通过定义线状光谱与连续谱的光强比, 定量地表征了线状光谱在总光谱中的相对强度, 并给出了驱动声压对各跃迁谱线光强比的影响. 关键词： 单泡声致发光 驱动声压 线状光谱 光强比     

基态O和D原子的低能弹性碰撞及OD（X2Π）自由基的准确解析势与分子常数

利用CCSD（T）理论及相关一致五重基aug-cc-pV5Z构建了OD（X²Π）自由基的相互作用势, 计算了这个自由基的光谱常数D₀, D_e, R_e, ω_e, ω_eχe及B_e, 其值分别为44574,46225?eV,009702 nm, 2724923,453534和100096 cm^-1, 均与实验结果相符很好. 利用这一相互作用势, 在绝热近似下通过数值求解双原子分子核运动的径向薛定谔方程, 找到了J=0时OD（X²Π）自由基存在的全部23个振动态, 完整地求出了每一振动态的振动能级、振动经典转折点、惯性转动常数和离心畸变常数, 其值与实验结果相当一致. 在10×10^-11—10×10^-3a.u.的能量范围内研究了基态O和D原子沿OD（X²Π）势能曲线的弹性碰撞, 计算了这一碰撞的总截面和各分波截面, 分析了各分波截面对总截面的不同贡献. 结果表明: 总截面的形状主要由s分波截面决定, 尽管直到l = 12的其他分波截面均有形状共振存在, 但由于其强度较弱, 大都湮没在较强的s分波截面中. 关键词： 弹性碰撞 总截面 形状共振 光谱常数     

LiAl分子基态、激发态势能曲线和振动能级

利用单双激发多参考组态相互作用方法获得了LiAl分子基态X¹∑⁺及七个激发态a³∏, A¹∏, b³∑⁺, c³∑⁺, B¹∏, C¹∑⁺, d³∏的势能曲线, 通过势能曲线得到各态的平衡核间距R_e, 进而求得绝热激发能和垂直激发能.计算结果表明:c³∑⁺ 电子态是一个不稳定的排斥态, A¹∏态是一个较弱的束缚态, 其余6个电子态均为束缚态; b³∑⁺与 c³∑⁺态之间存在预解离现象; 8个电子态分别解离到两个通道, 即Li(²S)+Al(²P⁰)与Li(²P⁰)+Al(²P⁰). 接着将势能曲线拟合到Murrel-Sorbie解析势能函数形式, 据此获得各态的光谱数据:基态X¹∑⁺的平衡键长为0.2863 nm, 谐振频率为316 cm^-1, 解离能D_e为1.03 eV, 激发态a³∏, A¹∏, b³∑⁺, c³∑⁺, B¹∏, C¹∑⁺, d³∏的垂直激发能依次为0.27, 0.83, 1.18, 1.14, 1.62, 1.81, 2.00 eV; 解离能依次为1.03, 0.82, 0.26, 排斥态, 1.54, 1.10, 0.93 eV, 相应谐振频率 ω_e为339, 237, 394, 排斥态, 429, 192, 178 cm^-1. 通过求解核运动的薛定谔方程找到了J=0时 LiAl分子7个束缚电子态的振动能级和转动惯量. 关键词： LiAl 光谱常数 势能曲线 振动能级     

MgH分子X2Σ+，A2Π和B2Σ+电子态的势能函数

利用QCISD(T),SAC-CI方法和cc-pVQZ,aug-cc-pVTZ,6-311++G及6-311++G(3df,2pd)基组,对MgH分子的基态X²Σ⁺,第一简并激发态A²Π和第二激发态B²Σ⁺的结构进行优化计算.通过对4个基组计算结果进行比较,得出6-311++G(3df,2pd)基组为最优基组.使用 关键词： 分子结构与势能函数 激发态 Murrell-Sorbie函数 C₆函数')" href="#">Murrell-Sorbie+C₆函数     

N2O异构体结构与解析势能函数

在B3P86/cc-PVTZ水平上,对N₂O异构体进行优化计算,得出N₂O基态的单重态能量最低,其稳定构型为C_∞v构型,平衡核间距R₁=0.1121nm,R₂=0.1177nm,α＝180°,能量为-185.1188a.u.同时计算出基态的简正振动频率ω₁(Π)=601.5010 cm^{关键词： 异构体 多体项展式理论 解析势能函数}     

NaZnLa(PO4)2中Ce3+和Tb3+的发光

采用高温固相反应合成了NaZnLa(PO₄)₂中掺杂Ce³⁺、Tb³⁺的荧光体,对其晶体结构、发光行为进行了研究,并尝试对NaZnLa(PO₄)₂:Ce,Tb荧光体进行调制。NaZnLa(PO₄)₂是LaPO₄的同构物,为单斜晶系独居石结构,从XRD谱数据得到NaZnLa(PO₄)₂基质的晶胞参数为a=0.6823nm,b=0.7045nm,c=0.6497nm,β=1039°,v=0.303nm³,其晶胞参数与单斜LaPO₄的晶胞参数相似。在NaZnLa(PO₄)₂:Ce,Tb荧光体中,Ce³⁺对Tb³⁺有良好的敏化作用,掺杂适量的BO₃^3-、Al³⁺、Dy³⁺,可以增强发光亮度。     

High resolution laser excitation spectroscopy of barium monosulfide

High-resolution spectra of BaS were recorded using laser excitation spectroscopy. BaS molecules were synthesized in a Broida-type oven. The observed rotationally-resolved spectrum of BaS in the 12 100–12 765 cm^?1 spectral range contains the 2-1, 3-1, 3-2, 4-2, 5-2, 5-3 vibrational bands of the A′¹Π–X¹Σ⁺ transition and the 4-1, 5-1, 5-2 vibrational bands of the a³Π₁–X¹Σ⁺ transition. Approximately 1000 lines of the A′¹Π–X¹Σ⁺ transition and 600 lines of the a³Π₁–X¹Σ⁺ transition for the main isotopologue ¹³⁸Ba³²S (67.5% natural abundance) were measured. Rotational and vibrational parameters were derived for the A′¹Π and a³Π₁ states.     

射流冷却AlO自由基B2Σ+—X2Σ+光谱研究

利用铝电极放电产生的Al原子与O₂反应生成AlO自由基,在超声射流冷却下在43 0—480nm波长范围观测到AlO自由基B—X跃迁的激光诱导荧光激发谱.光谱振动结构分析表明 所有的谱带属于V′-V″=1,2,3跃迁,并获得基态和激发态的振动频率与非谐性常数.另外还 对其中(1,4)谱带的转动结构进行标识,并得到相应的转动常数和离心畸变系数.对从基态 振动能级V″=5向上跃迁的谱带强度增强进行了讨论. 关键词： 光谱 AlO     

Jet-cooled laser-induced fluorescence spectroscopy of B2Σ+–X2Σ+ system of scandium monoxide: Improved molecular constants at equilibrium

The investigation on B²Σ⁺–X²Σ⁺ system of ScO was extended to higher vibrational levels by laser-induced fluorescence (LIF) spectroscopy in a free-jet. We have observed rotationally resolved excitation spectra for (4,0), (3,0), (2,0), and (1,2) bands in addition to the previously observed (0,0) and (1,0) bands. The wavenumbers of these bands were fitted to a Hamiltonian matrix to determine the molecular constants for the vibrational levels up to ν′=4 of the B²Σ⁺ state and ν″=2 of the X²Σ⁺ state. In addition, the vibration constants of the ground states were determined from the dispersed fluorescence wavenumbers between B²Σ⁺ (ν′=0–4) and X²Σ⁺ (ν″=0–8) transitions. The equilibrium molecular constants, derived from the extensive set of molecular constants for individual vibrational levels, were used to construct RKR potential energy curves for both the electronic states. The Franck–Condon factors were also calculated for the B²Σ⁺–X²Σ⁺ transition.     

The ultraviolet absorption spectra of GeO in rare gas matrices

The absorption spectra of GeO isolated in rare gas matrices have been investigated in the wavelength region 1150–3000 Å using the 2.5-GeV synchrotron in Bonn as a continuum light source. Two vibrational progressions of bands have been found in each of the matrices, in neon, argon, krypton, and xenon. These progressions are situated in the regions 2400–2700 and 1800–2100 Å. They have been analyzed as corresponding to gas-phase bands of the A¹Π-X¹Σ⁺ and the E¹Σ⁺-X¹Σ⁺ systems, respectively. Absorption lines of matrix-isolated GeO were also found in the region 1180–1500 Å.     

Extension of the A1Σ+-X1Σ+ system of7LiH near the dissociation limit

The absorption spectra of⁷LiH have been photographed in the 3,500?2,900 Å region using the second order of a 3.4 M Ebert spectrograph. Observations comprise previously observedA ¹ Σ ⁺-X ¹ Σ ⁺ transitions and several new vibrational bands of this system near the ionisation limit. Rotational and vibrational analysis of these bands (16≦V′≦20) have been carried out and the rotational constants for the upper states have been determined.     

The laser-induced fluorescence spectroscopy of gold monoxide: B2Σ−－X2Π3/2 transition

The electronic spectrum of the gaseous gold monoxide molecule has been investigated in the range of 16000－18500?cm^?1 using laser induced fluorescence spectroscopy and single vibronic level emission spectra. Five rotationally resolved vibronic bands are observed and assigned to the transitions B²Σ^? (v'?=?0－4) －X²п_3/2 (v''?=?0), in which the 0－0 transition is observed for the first time. The molecular constants of the excited state B²Σ^? are obtained by a rotational analysis of the spectra. The spin-orbit coupling constant and the vibrational constants of the ground state X²п_i are determined with the accuracy improved by one order of magnitude. The lifetimes of most observed bands are also measured for the first time.     

Comparison of photoelectron intensities and Franck-Condon factors in the photoionization of H2, HD and D2

The relative intensities of vibrational bands corresponding to the photoionization reactionX¹Σ_g⁺(υ″ = 0) + hv → X²Σ_g⁺(υ′ = 0, 1, 2 …) + e^? have been measured for H₂, HD and D₂, using He I radiation and a cylindrical mirror analyzer. These relative intensities differ significantly from squared overlap integrals (Franck-Condon factors) based on accurate potential curves for X¹Σ_g⁺ and X²Σ_g⁺, but are in good agreement with calculations performed by Itikawa which include the variation of transition moment with internuclear distance and the kinetic energy of the departing electron.     

Emission spectrum of MgCl molecule in 5030-4380Å

The emission spectrum of diatomic magnesium chloride molecule has been reinvestigated in the region 5030-4380 Å (B ²Σ⁺ —A ²Π transition) at a higher dispersion. The vibrational assignments of the bands are confirmed by observing the vibrational isotope shifts due to isotopes of magnesium and chlorine. Precise values of the vibrational constants are determined for theB ²Σ⁺ state.     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.