NO2分子的光学-光学双色双共振多光子离化谱

以Nd:YAG激光器的二倍频输出光为抽运光，其三倍频输出抽运的光学参量发生/放大器输出光为探测光，利用光学-光学双色双共振多光子离化光谱技术(OODR-MPI),获得了NO₂分子在605—675nm探测光波长范围内的多光子离化激发谱. 通过对NO₂分子离化机理的分析，确定了在此波长区间，NO₂分子经1+3+1双共振多光子过程离化，离化通道为NO₂(X²A₁)hν     

NO2分子的光学-光学双色双共振多光子离化谱

以Nd:YAG激光器的二倍频输出光为抽运光,其三倍频输出抽运的光学参量发生/放大器输出光为探测光,利用光学-光学双色双共振多光子离化光谱技术(OODR-MPI),获得了NO2分子在605-675 nm探测光波长范围内的多光子离化激发谱.通过对NO2分子离化机理的分析,确定了在此波长区间,NO2分子经1 3 1双共振多光子过程离化,离化通道为NO2(X2 A1)→hv1NO2(A2 B2)→3hv2NO2(3pσu)→hv2NO2 e.谱线归属结果表明,所得OODR-MPI谱对应于NO2分子3p%里德伯态的三光子共振吸收,获得了该态的对称伸缩振动频率ω1=(1442.5±25.5)cm-1,弯曲振动频率ω2=(590.5±4.9)cm-1,其带源位于(58331±71)cm-1处,量子亏损值为0.69.     

NO2分子里德堡态的光学-光学双共振多光子离化谱

采用光学-光学双共振多光子离化（Optical-optical double-resonant multiphoton ionization，简称OODR-MPI）技术详细研究了NO2分子里德堡态的能级结构。结果显示，用不同强度的激光作抽运光，尽管NO2分子的OODR-MPI谱均由规则的光谱序列组成，但NO2分子的离化通道存在很大区别，当抽运光强度较高时，NO2分子通过(3+1+1)双共振多光子过程离化；而当抽运光强度较低时，NO2分子通过(1+2+1)双共振多光子过程离化，两种离化机制的最终共振能级属于不同的里德堡态。     

NO(3+1)共振增强的多光子离化谱

用皮秒脉冲高功率Nd∶YAG激光器抽运的光学参量发生/放大器作激发源,获得了NO分子在420～500 nm波长范围内的多光子离化谱,光谱图呈现分离谱的特征,表明在该波长区间NO分子以多光子共振方式离化。离化信号随激光强度的近四次方变化关系表明,在420～500 nm波长范围内NO分子吸收4个光子而离化。通过对谱线的标识,首次分离出NO分子以E 2Σ激发电子态为中间共振态的(3+1)多光子离化光谱序列,由谱线序列峰值波长得到NO分子E 2Σ电子态的振动常数,从而实现了采用多光子离化技术对该态能级结构的实验研究。     

气体吸附对V掺杂石墨烯电子结构与光学性质的影响

基于密度泛函理论(DFT)的广义梯度近似(GGA),采用第一性原理方法研究了气体分子吸附对V掺杂石墨烯的吸附能、电子结构与光学性质的影响．能带结构计算表明:吸附NO₂分子的V掺杂石墨烯的带隙显著增加,从0 e V变为0.368 e V,由金属性转变为半导体特性,而吸附CO与NH₃分子的V掺杂石墨烯的带隙则变化很小．三种吸附构型(NO₂,CO,NH₃)的吸附能分别为-8.499 e V、-2.05 e V和-2.01e V,说明V掺杂石墨烯对NO₂气体分子吸附最强．进而计算了本征、V掺杂石墨烯及其吸附NO₂分子的光学性质,结果表明:随着V掺杂与吸附NO₂气体,石墨烯介电吸收峰值有所增大,介电峰位向低能量区域移动;本征石墨烯仅吸收紫外光,V掺杂石墨烯吸附NO₂分子可以明显拓宽光吸收的光谱范围;掺杂与吸附使得石墨烯光电导率显著增强,能在红外与可见光区产生光电流．上述结果表明V掺杂石墨烯吸附NO₂后...     

NaNO2晶体线性和非线性光学系数的计算

使用从头计算平面波赝势方法,计算了NaNO₂晶体电子能带结构,并使用改进的倍频公式计算了它的线性折射率和静态二级非线性系数,所得到的结果和实验值相符.采用实空间原子切割方法分析了阳离子和阴离子基团对光学性质的贡献.计算表明(NO₂)-基团对双折射率和倍频系数的贡献占主要地位,从而进一步验证了阴离子基团理论的正确性 关键词： 电子结构 非线性光学系数 从头计算方法     

高效率内腔式2 μm简并光学参量振荡器

报道了一种高效率的2 μm光学参量振荡器. 利用1.064 μm声光调Q Nd:YVO₄激光器抽运基于氧化镁掺杂周期性极化铌酸锂的内腔式光学参量振荡器, 在简并状态实现了稳定高效的2 μm激光输出. 当808 nm激光二极管抽运功率为20 W, Q开关工作频率为15 kHz时, 产生了平均功率为3.5 W、脉冲宽度为1.4 ns的2 μm激光, 光-光转换效率为17.5%, 斜效率为25%. 据我们所知, 该转换效率在2 μm波段内腔式光学参量振荡器中是最高的.     

铷原子双共振激发态光抽运光谱及其在1.5μm半导体激光器稳频中的应用

本文介绍分别采用双共振光抽运(DROP)和光学双共振(OODR)光谱技术获得铷原子激发态5P_3/2-4D_3/2 (4D_5/2)之间的超精细跃迁光谱.与传统的OODR光谱相比,DROP光谱在信噪比、线宽等方面具有明显的优势.当1 529 nm光栅外腔半导体激光器的频率采用DROP光谱锁定于～87Rb原子的5P_3/2(F'=3) -4D_3/2(F"=3)超精细跃迁线时,300 s内典型的残余频率起伏为～0.65 MHz;明显优于采用OODR光谱锁频的结果(300 s内典型的残余频率起伏为～1.8 MHz).     

H_2S里德堡序列共振增强多光子离化光谱

以纳秒Nd∶YAG脉冲激光器三倍频(355nm)激光抽运的染料激光器为激发光源,在484~520nm波长范围内,采用共振增强多光子离化光谱(REMPI)方法,对H2S分子里德堡序列的能级特性进行了实验研究,得到了谱峰间隔随激光波长增长而呈近二倍变化的两套谱峰序列嵌套而成的规则序列。该谱峰序列对应于H2S分子的里德堡序列激发。依据H2S分子低位激发电子态及里德堡序列的势能高度,可将离化过程确定为五光子4+1离化过程。并将所得到强谱峰序列归属为集结于珦H态的np(n=5,6,7,8)里德堡序列,将弱谱峰序列归属为集结于珟D态的ns(n=6,7,8)里德堡序列。两套序列的量子亏损分别为δ1=0.92和δ2=1.52。所得结果对H2S分子的光学检测及光谱特性研究具有重要意义。     

过渡金属Cu、Cr掺杂TiO2表面氧化性气体NO2光学气敏传感特性

采用密度泛函理论（DFT）体系广义梯度近似（GGA）第一性原理平面波超软赝势方法,分析锐钛矿型TiO₂（101）表面吸附NO₂分子光学气敏传感的微观机理.结果表明：Cu和Cr原子易于掺入TiO₂（101）表面,掺杂表面能稳定地吸附NO₂分子且吸附后光学性质发生显著变化.表面吸附NO₂分子后,Cu掺杂TiO₂（101）表面对分子的吸附能最大,吸附后结构更稳定,分子与表面的距离最短.通过分析差分电荷密度和电荷布居数发现,NO₂分子与基底表面间发生电荷转移,转移电子数目：Cu掺杂表面 > Cr掺杂表面 > 无掺杂表面.对比吸收光谱和反射光谱发现,在Cu掺杂表面吸附分子后,光学性质变化最明显,说明表面与吸附分子间氧化还原能力是决定光学气敏传感性能的核心因素.在过渡金属中,Cu与Cr都有4s价电子结构,其4s电子降低了材料表面氧空位的氧化性,增加了其还原性.对于氧化性气体,可以提升表面与分子的氧化还原作用,而Cu的4s电子更加活泼,从而光学气敏传感特性更加明显.因此,Cu掺杂的TiO₂对氧化性气体是一种较好的光学气敏传感材料.     

332—362nm范围内CF2Cl自由基的共振增强多光子电离研究

用CF₂Cl₂分子直流脉冲放电的方法产生CF₂Cl自由基，结合共振增强多光子电离(REMPI)技术，测量了332—362nm波长范围内CF₂Cl自由基的(2+1)REMPI光谱，分析并标识了4s Rydberg态带源位于(ν_0—0=55371cm^-1)，两个被激活振动模ω′₃(CF₂剪式振动模)和ω₄′(OPL 关键词：     

Dynamics mechanism of optical-optical double-resonant multiphoton ionization of nitrogen dioxide

The optical-optical double-resonant multiphoton ionization (OODR-MPI) spectrum of NO2 molecule in the 460-605-nm wavelength region of the probe photon is presented. The mechanism of the OODR-MPI of NO2 molecule is analyzed. The results show that the resonant features can be assigned to the transitions from the first 3sσg Rydberg intermediate resonant state to the final npσu Rydberg series. The ionization pathway is NO2 (X2A1) 3hv1→ 3sσghv2→npσu hv2 or autoionization→NO2+ + e. It is found that the converging potential of the npσu Rydberg series and the quantum defect of np orbit about NO2 are (78803 ± 14) cm-1 and 0.652 ± 0.014, respectively. The bending vibration frequency of 5pσu state is determined also.     

Experimental determination of the potential energy curves of the I(3/2u) and I(3/2g) states of Kr+ 2

The I(3/2u) and I(3/2g) states of Kr⁺ ₂ have been investigated by pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy following (2 + 1′) resonance-enhanced multiphoton excitation via the 0⁺ _g Rydberg state located below the Kr?([4p]⁵5p[1/2]₀) + Kr(¹S₀) dissociation limit of Kr₂. From the positions of a large number of vibrational bands in the spectra of the ⁸⁴Kr₂ and ⁸⁴Kr-⁸⁶Kr isotopomers, the adiabatic ionization potentials (IP(I(3/2u)) = 112672.4 ± 0.8cm^?1, IP(I(3/2g)) = 111 395.0 ± 1.4cm^?1), the dissociation energies (D ⁺ ₀(I(3/2u)) = 368.8 ± 2.0cm^?1, D ⁺ ₀(I(3/2g)) = 1646.2 ± 2.3cm^?1) and vibrational constants for both ionic states have been determined. Potential energy curves have been extracted which perfectly reproduce all experimental observations and are accurate over a wide range of energies and internuclear distances. The equilibrium internuclear distances (R ⁺ _e(I(3/2u)) = 4.11 ± 0.04 Å, R ⁺ _e(I(3/2g)) = 3.35 ± 0.10 Å) have been derived by comparing the intensity distribution in the PFI-ZEKE photoelectron spectra to calculated Franck-Condon factors. The dissociation energy of the I(3/2g) state and the equilibrium internuclear distance of the I(3/2u) state differ markedly from previously reported values.     

Proton conductivity and ferroelectric phase transition in hydrogen-bonded ferroelectric NH4IO3

We report on the ac dielectric permittivity (ε) and the electric conductivity (σ_ω), as function of the temperature 300?K?T4IO₃. The main feature of our measured parameters is that, the compound undergoes a ferroelectric phase transition of an improper character, at (368?±?1)K from a high temperature paraelectric phase I (Pm2₁ b) to a low temperature ferroelectric phase II (Pc21n). The electric conduction seems to be protonic. The frequency dependent conductivity has a linear response following the universal power law (σ_{( ω )}?=?A(T)ω ^{s (T)}). The temperature dependence of the frequency exponent s suggests the existence of two types of conduction mechanisms.     

碘分子单频及双频多光子光谱

采用多光子离化谱和荧光激发谱技术，对碘分子单频和双频五光子离化谱和三光子荧光谱进行了研究和标识．对OODR五光子离化谱中一组间隔为72cm^-1的振动序列进行了归属，并确定了其激发、发射和离化通道 关键词：     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数     

The multiphoton ionization spectrum of jet-cooled pyrimidine in the 3p Rydberg and B1 (π,n) states

Resonance-enhanced multiphoton ionization (REMPI) has been applied to study the n → 3p Rydberg transition of pyrimidine (jet-cooled sample and mass resolved spectrum). Only the one component, the 3p_z(B₂), appears in the (2 + 1) REMPI and the active vibrations are ν_6a = 622, ν₁ = 946, and ν_9a = 1116 cm⁻¹. The symmetry of the state was determined by polarization measurements (linear, circular polarization). The first (π^∗,n) ³B₁ triplet state appears as a one-photon resonance in the three-photon ionization process.     

Analysis of rotational structure in the high-resolution infrared spectrum and assignment of vibrational fundamentals of butadiene-2,3-C2

The 2,3-¹³C₂ isotopomer of butadiene was synthesized, and its fundamental vibrational fundamentals were assigned from a study of its infrared and Raman spectra aided with quantum chemical predictions of frequencies, intensities, and Raman depolarization ratios. For two C-type bands in the high-resolution (0.002 cm⁻¹) infrared spectrum, the rotational structure was analyzed. These bands are for ν₁₁ (a_u) at 907.17 cm⁻¹ and for ν₁₂ (a_u) at 523.37 cm⁻¹. Ground state and upper state rotational constants were fitted to Watson-type Hamiltonians with a full quartic set of centrifugal distortion constants and two sextic ones. For the ground state, A₀ = 1.3545088(7) cm⁻¹, B₀ = 0.1469404(1) cm⁻¹, and C₀ = 0.1325838(2)  cm⁻¹. The small inertial defects of butadiene and two ¹³C₂ isotopomers, as well as for five deuterium isotopomers as previously reported, confirm the planarity of the s-trans rotamer of butadiene.     

A rotationally-resolved Rydberg transition of I2

Rotationally-resolved bands leading to a Rydberg state R 0 _u ⁺ of molecular I₂ are observed in a two-stage, three-photon transition from the ground state. The R 0 _u ⁺ state interacts homogeneously with high vibrational levels, ν_F ≈ 200–250, of an ionic state F 0 _u ⁺, the perturbation being directed by the vibrational overlap integrals towards even-numbered vibrational levels of R. Spectral constants of R 0 _u ⁺ are (in cm^-1): T _e = 61665·15, ω_e = 209.29, ω_e x _e = 0·859, B _e = 0·03842 and α_e = 1·6 × 10^-4. The electronic matrix element for the R, F interaction (excluding one deviant result) is |W _e| = 107 ± 1 cm^-1; thus W _e/ω_e ≈ 0·5, corresponding to ‘intermediate’ coupling. Energy considerations indicate that R should be assigned to the 0 _u ⁺ state of either the configuration (2430 Π_1/2g )6pσ _u , or of (2421 ⁴Σ _u ^-)6sσ _g . This state is the first extra-valence state of I₂ to be rotationally analysed.