氧分子离子第一负带系（b^4∑g^——α^4Пu）（2，6）带的光谱测量与分析

采用光外差-速度调制分子离子吸收光谱技术，在近红外波段13170-13500cm^-1范围内，对氧分子离子第一负带（b^4∑g^--α^4Пu）（2，6）带进行测量和分析，有关第一负带（2,6）带光谱测量尚未见文献报道．本文简述了光外差-速度调制光谱技术的特点，同时给出了对复杂四重态跃迁谱带的分析，运用非线性最小二乘拟合获得了该跃迁上下态精确的分子常数。     

CO+分子离子彗尾带系在近红外区域的光谱研究

CO 分子离子是一种重要的瞬态自由基分子,许多研究者对该带系进行了大量的研究。文章采用光外差-磁旋转-速度调制光谱技术测量了12C16O 分子离子彗尾带系(A2Πi-X2Σ )在近红外区域的3个支带(0,3),(1,4)和(3,6)的振转吸收光谱。利用最小二乘法拟合,得到了上态A2Πi(ν′=0,1,3)的精确的分子常数。进一步验证了光外差-磁旋转-速度调制光谱技术在吸收光谱测量中的优越性。     

氧分子离子A2∏u-X2∏g态转动光谱分析

利用光外差-速度调制吸收光谱技术,测量了氧气分子离子在11385～12100 cm^-1的多普勒分辨吸收光谱,获得的谱线被指认到该分子离子第二负带的(2,19)、(3,20)、(5,21)跃迁谱带．利用全局拟合方式,得到了涉及能级的精确分子常数．     

CO三重带系d^3Δ-α^3∏（4，0）和（5，0）带激光光谱研究

光外差磁旋转浓度调制激光光谱技术属于一种高灵敏度的吸收光谱测量方法，可以用于瞬态分子和激发态分子光谱的检测。采用这种技术分别在16400～16650cm^-1和17450～17750cm^-1波段内直接观测到CO三重带系d^3△←α^3∏(4，0)(5，0)振转吸收光谱。这种跃迁的上态d^3△1(v=4)，d^3△2(v=4)，d^3△1(v=5)分别与A^1∏(v=0)，D^1△(v=0)和A^1∏（v=1)态存在微扰相互作用。通过对所测量到的CO三重带系(4，0)(5，0)振转谱带作了包含微扰相互作用在内的分析，获得了上态d^3△(v=4，5)的精确的分子转动光谱常数。     

CO三重带系d3Δ-a3Π(4,0)和(5,0)带激光光谱研究

光外差磁旋转浓度调制激光光谱技术属于一种高灵敏度的吸收光谱测量方法 ,可以用于瞬态分子和激发态分子光谱的检测。采用这种技术分别在 16 4 0 0～ 16 6 5 0cm-1和 174 5 0～ 1775 0cm-1波段内直接观测到CO三重带系d3 Δ←a3 Π(4,0 ) (5 ,0 )振转吸收光谱。这种跃迁的上态d3 Δ1(v =4 ) ,d3 Δ2 (v =4 ) ,d3 Δ1(v =5 )分别与A1Π(v =0 ) ,D1Δ(v =0 )和A1Π(v =1)态存在微扰相互作用。通过对所测量到的 CO三重带系 (4,0 ) (5 ,0 )振转谱带作了包含微扰相互作用在内的分析 ,获得了上态d3 Δ(v =4 ,5 )的精确的分子转动光谱常数。     

NO分子b~4Σ~-—a~4Π_i(4,0)带的吸收光谱

通过对NO与He流动混合气体放电,产生了激发态的NO(a⁴Ⅱ_ii)分子.利用光外差-浓度调制吸收光谱技术测量了NO分子在12530-12850 cm^-1波段内的吸收光谱,并标识出b⁴∑^--a⁴Ⅱ_i（4,0）带在该波段内的324条跃迁谱线.采用标准⁴∑^-—⁴Ⅱ_i哈密顿量模型,通过非线性最小二乘法拟合其中267条谱线,拟合残差(0.0071 cm^-1)接近实验系统测量误差(0.007 cm^-1).获得的主要分子常数与文献提供的常数符合,并且拟合得到了精细结构分子常数.     

NO分子b4∑--a4∏i（4，0）带的吸收光谱

通过对NO与He流动混合气体放电,产生了激发态的NO（a4∏ii）分子．利用光外差-浓度调制吸收光谱技术测量了NO分子在12530-12850cm-1波段内的吸收光谱,并标识出b4∑--a4∏i（4,0）带在该波段内的324条跃迁谱线．采用标准4∑--4∏i哈密顿量模型,通过非线性最小二乘法拟合其中267条谱线,拟合残差（0．0071cm-1）接近实验系统测量误差（0．007cm-1）．获得的主要分子常数与文献提供的常数符合,并且拟合得到了精细结构分子常数．     

利用法布里-珀罗腔抑制电光相位调制中的剩余幅度调制

激光经电光相位调制后,由于剩余幅度调制的存在造成调制边带幅度不相等。利用法布里-珀罗腔的透射特性和Pound-Drever-Hall技术对通过法布里-珀罗腔的调制光正、负一级边带的幅度产生不同的衰减,使得调制边带的幅度相等,从而实现对电光相位调制中剩余幅度调制的抑制。采用该方法,理论上计算了调制光经法布里-珀罗腔后的光外差光谱信号,获得锁定法布里-珀罗腔后调制边带幅度的不对称度较腔锁定前减小四个数量级。实验研究了调制光经法布里-珀罗腔透射的光外差光谱,结果表明将法布里-珀罗腔锁定于该透射光外差光谱中心零位时,对剩余幅度调制的抑制程度可达45 dB。     

N2+分子离子A2∏u-X2∑+g 系(2,0)带光外差速度调制光谱

采用光外差速度调制光谱技术研究了N2+分子离子A2∏u-X2∑+g 系(2,0)带转动光谱．由于所用技术的高灵敏度特性，精确地确定了该带310条谱线的频率，其中，那些重叠谱线的频率也通过解谱精确地确定了．利用标准Hamilton量，采用非线性最小二乘方法对该带进行了分析，获得了最精确的分子常数．     

激光光谱学

O433.54 2004004057 光外差磁旋转速度调制光谱技术的参量优化=Optimization of optical heterodyne magnetic rotation enhanced velocity modulation spectroscopy[刊,中]/甘雨洁(华东师范大学物理系,光谱学与波谱学教育部重点实验室.上海(200062)),李伟…∥量子电子学报.—2004,21(3).—295-301 光外差磁旋转速度调制光谱技术是一种对离子分子选择性测量的高灵敏激光吸收光谱技术。本文将以N_2~ 和CO~ 为例,主要讨论该技术的高灵敏度和高信噪比的特点,分析影响实验结果的各个参量,介绍光谱信号测量中的优化过程。图9参16(杨妹清)     

The ν2 + ν4 band of 12CF4

From a high-resolution diode laser spectrum of cooled ¹²CF₄, line assignments in ν₂ + ν₄ at 1066.4 cm^?1 have been made for tetrahedral subspecies to J = 20, and in many cases to higher J. Spectroscopic constants have been obtained from a least-squares fit of the Hamiltonian, and the relative intensities of the assigned lines have been calculated. The ground- and excited-state rotational constants, Coriolis constant, and splitting of the F₁ and F₂ vibrational substates have the values a.The CF bond length in the ground vibrational state is thus $\text{r}{}_0\text{= 1.31752 ± 0.00007}\text{A}\text{?}$. The analysis of a combination band such as this provides a method of obtaining ground-state spectroscopic constants of spherical-top molecules directly from the infrared spectrum, without the necessity of measuring weak “forbidden” transitions. The assignments allow accurate predictions of the frequencies emitted by the CO₂-pumped CF₄ laser.     

Narrow band model parameters for the CO2 4·3 μm band

The narrow band model parameters of the carbon dioxide 4·3 μm band have been obtained from absorption experiments with four broadening gases, namely CO, N₂, O₂, and Ar. The temperature and wave number dependence of the parameters are discussed. The experiments were performed at temperatures of about 303, 598 and 1185°K, with CO₂ partial pressures between 0·01 and 1·0 atm, at a total pressure of 1·0 atm. The Elsasser and the statistical models were applied to thebands in order to obtain applicable parameters and to determine a suitable model for the band at each temperature. It has been found that the Elsasser model is an adequate representation of the band at low temperatures whereas the statistical model is preferred at elevated temperatures. The effect on the line half-widths of the broadening gases is discussed. Good agreement is obtained between absorptance calculated with the present parameters and experimental results obtained by other authors.     

Raman band shapes and the dynamics of liquid N2O4

The Raman spectra of the totally symmetric A _g modes, v ₁, v ₂ and v ₃, of the N₂O₄ molecule have been measured in the liquid state at 262, 279 and 297 K. The vibrational and the rotational correlation functions are calculated. The long-time exponential decay of the rotational correlation functions of all the A _g modes reflects an asymptotic diffusional behaviour of molecular reorientation. The rotational relaxation rate is found to increase with increasing temperature. A marked point of inflection from the short time inertial correlation to the long time exponential decay appears at about 0·35 ps for the v ₂ mode. This is an indication of orientational rebound arising from the librational motion in a temporary solvent cage. The isotropic bandwidth increases in the order v ₁ < v ₂ < v ₃, which is also the order of decreasing vibrational frequency. The temperature dependence of the peak frequency and of the bandwidth are also found to increase in the same order. These observations are analysed qualitatively in terms of two models of vibrational dephasing which take into account the effect of vibrational anharmonicity.     

Optical properties and electronic band structure of CdGa2Te4

Optical properties of a defect-chalcopyrite-type semiconductor CdGa₂Te₄ have been studied by optical absorption, spectroscopic ellipsometry (SE), and electroreflectance (ER) measurements. Optical absorption measurements suggest that CdGa₂Te₄ is a direct-gap semiconductor having the band gap of ∼1.36 eV at 300 K. The complex dielectric-function spectra, ε(E)=ε₁(E)+iε₂(E), measured by SE reveal distinct structures at energies of the critical points (CP's) in the Brillouin zone. ER spectrum facilitates the precision determination of the CP parameters (energy position, strength, and broadening). By performing the band-structure calculation, these CP's are successfully assigned to specific points in the Brillouin zone.     

Energy band structure of CdCr2Se4 by APW method

The results of the first band structure calculation of the CdCr₂Se₄ magnetic semiconductor are reported and discussed in connection with the experiment and band structure results for related nonmagnetic compounds. For the calculation, the unsymmetrized APW method has been chosen due to complexity of the problem as well as physical reasons.     

Measurement and analysis of the infrared absorption spectrum of the 2ν2 band of 12CH4

Approximately 500 infrared absorption lines with room-temperature strengths between 3 × 10^?5 and 1 × 10^?2 atm^?1 were assigned to the 2ν₂ band of ¹²CH₄ in the region from 2930 to 3250 cm^?1. These determine 207 of the 212 upper-state energy levels through J′ = 12 as well as a number of levels with J′ = 13 and 14. All but 17 of the levels with J′ ≤ 12 are calculated to 0.03 cm^?1 or better on the basis of a Hamiltonion that contains Coriolis and Fermi interaction terms coupling the upper states of the five bands, 2ν₄, ν₂ + ν₄, ν₁, ν₃, and 2ν₂.     

First-principles study of Cu2ZnSnS4 and the related band offsets for photovoltaic applications

First-principles calculations of the band offsets between Cu(2)ZnSnS(4) (CZTS) and XS (X = Cd, Zn) are performed. While the interface dipole contribution for the band offsets is calculated using the Perdew-Burke-Ernzerhof functional, the Heyd-Scuseria-Ernzerhof hybrid functional is employed to introduce the quasiparticle corrections to the band offsets. The calculated conduction band offset between CZTS and CdS is 0.2 eV, validating CdS for the buffer layer of the CZTS solar cell. The small conduction band offset stems from the band gap narrowing of CdS under the interface strain caused by the lattice misfit with CZTS. A large valence band offset over 0.9 eV between CZTS and ZnS indicates that precipitated ZnS is regarded as an inactive insulator phase in CZTS absorbers.     

Line assignments and intensities of the ν2 + ν3 − ν2 band of 12CH4

As part of a comprehensive effort to compile line parameters of methane from 2400 to 3200 cm^?1, the P and R branches of the ν₂ + ν₃ ? ν₂ band of CH₄ at 3010 cm^?1 were assigned through upper state J = 9. The process utilized the analysis of ν₂ + ν₃ at 4544 cm^?1 by J. C. Hilico, J. Degni, J. P. Champion, and G. Guelachvili (J. Mol. Spectrosc.81, 277–302 (1980)) and the ν₂ levels derived from the infrared spectrum by Margolis (in preparation) to predict the positions of the hot band. Experimentally determined lower-state energies were used to confirm assignments, and line intensities of the 300 transitions assigned are observed on the order of 10^?3 cm^?2 atm^?1 or less.