H280Se分子的26个振动带转动结构的全拟合分析

阐述了全拟合分析方法的理论基础,通过对Ｈ２８０Ｓｅ分子２４个已知转动结构振动带的３５１６个上态能级的全拟合分析,得到１１２个基本光谱参数,拟合偏差为１０．６×１０－３ｃｍ－１。用这套基本光谱参数精确预言了首次记录的Ｈ２８０Ｓｅ分子（５００,Ａ１）和（４０１,Ｂ２）局域模振动带的转动结构,并在简正模和局域模下分别拟合得到有效振转光谱参数。将归属得到的Ｈ２８０Ｓｅ分子（５００,Ａ１）和（４０１,Ｂ２）振动带的２５２个上态能级并入全拟合中,得到１１４个基本光谱参数,拟合偏差为９．６２×１０－３ｃｍ－１。     

CH^35Cl3和CH^35Cl2^37Cl分子V=3的傅里叶变换光谱研究

采用傅里叶变换光谱技术（ＦＴＳ）记录了ＣＨ＾３５Ｃｌ３和它的同位素分子ＣＨ＾３５Ｃｌ２＾３７Ｃｌ的Ｖ＝３的高分辨光谱，由于０．０２ｍ＾－１分经不足以分辨Ｋ结构，我们将所观察到的谱线近似归属为Ｋ＝０的转动能级，归属了ＣＨ＾３５Ｃｌ３岔子４〈Ｊ〈７３，ＣＨ＾３５Ｃｌ＾３７Ｃｌ分子６〈Ｊ〈５３的转动级。最后采用最小二乘法拟合，得到了关于Ｊ的转动常数和振动带心。     

自由基分子CN（A^2Пi—X^2Σ^＋）的光谱研究

利用塞曼调制磁旋转光谱技术对自由基分子ＣＮ（Ａ＾２ΠＩ－ｘ＾２Σ＾＋）（１２,６）带、（７,２）带进行了测量,标识了光谱并拟合了Ａ＾２Πｉ太分子常数,从而得到Ｖ＝７Ｔ Ｖ＝１２振转谱带的Ｔｖ、Ａｖ、Ｂｖ、Ｄｖ等参数,还获得Ａ双分裂参数Ｐｖ和ｑｖ,两个带的总拟合方差分别为０．０３９和０．０４６ｃｍ＾－１。     

CH3D分子3V2泛频态高分辨红外光谱的振动分析

用最小二乘法拟合ＣＨ３Ｄ分子６４２８ｃｍ＾－１附近振动带的１３８个能级，１０个振动常数。振动分析阐明带为ＣＨ３分子Ｃ－Ｄ对称伸缩振动３Ｖ２态，并与局域模振动理论计算值进行了比较。     

He（2^3S）与N2O（X）Penning电离中的N2O^＋（A^2Σ^＋）生成速率及相…

在分子束条件下测量了Ｈｅ（２＾３Ｓ）＋Ｎ２Ｏ（Ｘ）→Ｎ２Ｏ＾＋（Ａ＾２Σ＾＋）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－反应的Ｐｅｎｎｉｎｇ电离光学光谱，求得了Ｎ２Ｏ＾＋（Ａ＾２Σ＾＋）态的初生态相对振动布居。以Ｈｅ（２＾３Ｓ）＋Ｎ２（Ｘ）→Ｎ＾＋２（Ｂ＾２Σ＾＋ｕ）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－为参考反应，测量了Ｈｅ（２＾３Ｓ）＋ＢＮ２Ｏ＾＋（Ａ＾２Σ＾＋）＋Ｈｅ（＾１Ｓｏ）＋ｅ＾－反应的速率常数ＫＮ２Ｏ＾＋（Ａ）     

复合物o—C6H4F2.Ar的电子S1态的内部van der Waals振动

报道了复合物ｏ－Ｃ６Ｈ４Ｆ２．Ａｒ的电子Ｓ１态内ｖａｎ ｄｅｒ Ｗａａｌｓ（ｖｄｗ）振动的实验和理论研究。在超声束中,利用双光子共振电离光谱和飞行时间质谱技术,揭示了Ｓ１←Ｓ０电子态跃迁涉及内ｖｄＷ振动的３个谱带。光谱分析表明,一＋１６．１ｃｍ＾－１是Ａｒ沿ｏ－Ｃ６Ｈ４Ｆ２分子对称面内的振动模的基频跃迁。     

超声射流冷却SO2^—A2—^1A1激光诱导荧光激发谱

测得了３１５￣３３０ｎｍ超声射流冷却下ＳＯ２＾１Ａ２－＾１Ａ１激光诱导荧光（ＬＩＦ）激发谱，获得了７个有明显Ｋ结构的Ｃ型跃迁的转动子带分辨谱，并将７０个转动子带归属为（１，ｍ，１）－（０，０，０）和（０，ｎ，１）－（０，０，０）（４≤ｍ≤７，８≤ｎ≤１０）的跃迁带系。光谱分析得到ＳＯ２＾１Ａ２－＾１Ａ１跃迁的带源ｖ００、＾１Ａ２态弯曲振动频率ｖ′２，非谐性常数Ｘ２２′分别为（２７９５０±５）、（２     

2—（2′—羟基苯基）间氮杂氧茚放大的自发辐射效应的实验和理论研究

报道了在氮分子激光泵浦下，激发态分子内质子转移分子２－（２′－羟基苯基）间氮杂氧茚（ＨＢＯ）环己烷溶液放大的自发辐射（ＡＳＥ）实验和理论研究，在环己溶液中，ＨＢＯ的增益系数。（５１０ｎｍ）约为１．２ｃｍ＾－１，在建立了ＨＢＯ激发态分子内质子转移（ＥＳＩＰＴ）的放大的自发辐射动态模型基础上，通过数值模拟得到了ＨＢＯ的增益光谱和放大的自发辐射光谱计算结果与实验很好相符，证实了ＨＢＯ的酮式异构体的基态寿     

束—气条件下He（2^3S）＋CH2Cl2碰撞传能反应的动力学研究

本文在束－气条件下研究了亚稳态原子Ｈｅ（２＾３Ｓ）与ＣＨ２Ｃｌ２间的传能反应，测得了由该反应产生的ＣＨ（Ａ＾２△－Ｘ＾２П），ＣＨ（Ｂ＾２∑＾－Ｘ＾２П）ＣＨ（Ｃ＾２∑＾＋－Ｘ＾２П）和Ｈ原子（Ｂａｌｍｅｒ系）的化学发光光谱。通过对ＣＨ（Ａ，Ｂ）的光谱进行计算机模拟，推测出初手的ＣＨ（Ａ＾２△，ｖ＾１＝０－２）态振动分布为Ｎｏ：Ｎ１：Ｎ２＝１００：４０±５：１９±２，ＣＨ（Ａ＾２△，ｖ＾１＝０－０     

Br2分子里德堡态的高分辨转动谱研究

用窄线宽（０．０８ｃｍ＾－＾１）脉冲可调谐紫外激光和（２＋１）多光子电离方法测量了Ｂｒ２的里德堡（Ｒｙｄｂｅｒｇ）态光谱,在７００００－７１５００ｃｍ＾－＾１范围内,获得了溴分子［П３／２］４ｄ振动系列,测量（ｖ＇,ｖ”）＝（１,０）,（２,０）的高分辨振转谱,得到其转动常数Ｂ’７９－８１分别为０．０８８３２和０．０８８０５ｃｍ＾－＾１,并提出此系列的角动量量子数Ω应为１。     

High-Resolution Study of the nnu(2), n = 1, 2, 3, Vib-Rotational Bands of D(2)Se

High-resolution Fourier transform spectra of the D(2)(M)Se with M = 76, 77, 78, 80, and 82 in the regions of the first and second bending overtones 2nu(2) and 3nu(2) near 1480 and 2210 cm(-1), respectively, were recorded for the first time and assigned. On the basis of these experimental data, rotation-vibration energies were determined and fitted together with those of the (010) state reported earlier (W. Jerembeck, H. Bürger, J.-M. Flaud, and Ph. Arcas, J. Mol. Spectrosc. 197, 215-221 (1999)) by using the "Global Fit" procedure. The obtained set of 43 fitted parameters for these three vibrational states of the D(2)(80)Se species (altogether 86 fitted parameters for 12 states of five M species) reproduces the rotation-vibration energies of all studied states with accuracies close to experimental uncertainties. Copyright 2000 Academic Press.     

Analysis of the (0 0 v(3)), v(3) = 1, 2, 3 Vibrotational States of HDSe

High-resolution Fourier transform spectra of HDSe in the region of the 2nu(3) and 3nu(3) bands were recorded and analyzed for five different (M)Se isotopic HDSe species. Energies obtained from rovibrational analyses of the (002) and (003) states, together with those taken of the (001) state from an earlier study [O. N. Ulenov, G. A. Onopenko, N. E. Tyabaeva, H. Bürger, and W. Jerzembeck, J. Mol. Spectrosc. 198, 27-39 (1999)], were used as input information for a "Global Fit" procedure. This fit provided 34 spectroscopic parameters for the HD(80)Se species which reproduced rotational-vibrational transitions of the (001), (002), and (003) states within experimental accuracy. Corresponding analyses were performed for the other (M)Se (M = 82, 78, 77, and 76) species. Copyright 2000 Academic Press.     

High-resolution rotational analysis of HDS: 2ν3, ν2 + 2ν3, 3ν3, and ν2 + 3ν3 bands

High-resolution Fourier transform spectrum of the HD³²S molecule was studied in the region of 5000-9000 cm⁻¹. More than 1600 observed transitions yielded 239, 264, 131, and 116 upper state ro-vibrational energies of the states (002), (012), (003), and (013), respectively. With a Watson-type effective Hamiltonian model, the ro-vibrational parameters of these four upper states were determined by a least-square fitting which can reproduce the ro-vibrational energies close to the experimental accuracy. The relative linestrengths are also discussed.     

High-resolution study of the ν1 + ν2 and ν2 + ν3 strongly interacting bands of D2Se

A high-resolution Fourier transform spectrum of the D₂^MSe species (M = 82, 80, 78, 77, and 76) in the region 2300-2500 cm⁻¹ was recorded for the first time and assigned. On the basis of these experimental data, rotation-vibration energies of the (1 1 0) and (0 1 1) vibrational states were fitted, and band centers, and rotational, centrifugal distortion, and resonance interaction parameters were determined for the main D₂⁸⁰Se species. The obtained set of 32 fitted parameters reproduces the 647 rotation-vibration energies with a rms deviation of 0.00024 cm⁻¹. The ν₁ + ν₂ and ν₂ + ν₃ bands of the other four isotopic species are analyzed as well.     

Global fit of the high-resolution infrared spectrum of D2S

High-resolution Fourier-transform spectra of the D₂S molecule in the regions of polyads of interacting vibrational states v = 3/2, 2, 5/2, 3 and 7/2 (v = v₁ + v₂/2 + v₃) were recorded for the first time with a Bruker IFS 120 Fourier-transform interferometer and analysed. A global fit of all currently available rotation-vibration energies has been made for 22 vibrational states of the D₂S molecule. The resulting set of 231 parameters reproduces all the initial experimental data (about 3670 vibration-rotation energies which correspond to more than 9700 ro-vibrational transitions with J^max = 25) with accuracies close to the experimental uncertainties.     

High-Resolution Fourier Transform Spectra of HDSe: The Interacting States (v(1) v(2) v(3))/(v(1) +/- 1 v(2) -/+ 2 v(3)) with 2v(1) + v(2) = 1, 2, 3, and 4

For the first time, high-resolution Fourier transform spectra of HDSe in the region of the three polyads, nu(1)/2nu(2), nu(1) + nu(2)/3nu(2), and 2nu(1)/nu(1) + 2nu(2)/nu(2) + nu(3), have been recorded and analyzed. Combined with an earlier investigation of the nu(2) band, and including estimates for the unobserved "dark" 4nu(2) band, these levels were subjected to a "Global Fit," which makes use of relations between parameters within the different polyads. Since there are five isotopic species present in natural HD(M)Se (M = 82, 80, 78, 77, 76), altogether 34 vibration-rotation bands have been studied in the present contribution. The parameters determined by the Global Fit reproduce upper vibrational-rotational energies of all these bands with accuracies close to experimental precision. Copyright 2000 Academic Press.     

A refined potential energy function for the electronic ground state of H2Se

The potential energy surface for the electronic ground state of the hydrogen selenide molecule has been determined previously by Jensen and Kozin [J. Mol. Spectrosc. 160 (1993) 39] in a fitting to experimental data by means of the MORBID computer program. We report here a further refinement of this surface, also made with the MORBID program. With the refined potential surface, we can make predictions of rotation-vibration transition wavenumbers for H₂Se, D₂Se, and HDSe, and with these predictions we can assign weak spectra of these molecules. We assign here two very weak bands of HD⁸⁰Se, ν₁+ν₂+ν₃ and 2ν₁+ν₃. The refinement of the potential energy surface was made possible because (1) the number of vibrational states characterized experimentally for various isotopomers of H₂Se has approximately doubled since 1993, and (2) we now have access to larger computers with which we can fit energy spacings of states with J?8, whereas Jensen and Kozin could only use J?5. In the present work, we fitted rotation-vibration energy spacings associated with 24 vibrational states of H₂⁸⁰Se with v₁?6, v₂?3, and v₃?2; 11 vibrational states of D₂⁸⁰Se with v₁?2, v₂?3, and v₃?2, and 17 vibrational states of HD⁸⁰Se with v₁?3, v₂?3, and v₃?3. The input data set comprised 3611 energy spacings. In the fitting, we could usefully vary 29 potential energy parameters. The standard deviation of the fitting was 0.12 cm⁻¹ and the root-mean-square deviation for 49 vibrational term values was 0.59 cm⁻¹.     

Search for x-ray induced acceleration of the decay of the 31-yr isomer of (178)Hf using synchrotron radiation

Enhanced decay of the 31-yr isomer of (178)Hf induced by x-ray irradiation has been reported previously. Here we describe an attempt to reproduce this result with an intense "white" x-ray beam from the Advanced Photon Source. No induced decay was observed. The upper limits for the energy-integrated cross sections for such a process, over the range of energies of 20--60 keV x rays, are less than 2 x 10(-27) cm(2) keV, below the previously reported values by more than 5 orders of magnitude; at 8 keV the limit is 5 x 10(-26) cm(2) keV.     

Rovibrational Energies of Triatomic Molecules by Means of the Rayleigh-Schrödinger Perturbation Theory

A Rayleigh-Schr?dinger perturbation theory approach based on the adiabatic (Born-Oppenheimer) separation of vibrational motions was previously developed and used to evaluate for a system of coupled oscillators the adiabatic energy levels and their nonadiabatic corrections. This method is applied here to calculate rotation-vibration energies of the triatomic molecular ions HeH(+)(2) and ArNO(+) consisting of a strongly bound diatomic fragment and a relatively loosely bound rare gas atom. In these systems the high-frequency stretching motion of the diatomic fragment can be separated from the other two low-frequency motions without substantial loss of accuracy. Treating the diatomic fragment as a rigid rotor, the low-frequency stretching motion is decoupled from the bending motion in analogy to the concept of the adiabatic (Born-Oppenheimer) separation of motions and the strong nonadiabatic couplings between these two motions are accounted for perturbationally. Although the resulting perturbation series may show poor convergence, they turn out to be accurately summable by applying standard techniques for the summation of divergent series. Comparison with the results obtained from full-dimensional calculations for the two ions shows that the approach is capable of providing accurate energies for quite a few of the bound rotation-vibration states and that in the case of the HeH(+)(2) ion it is even able to predict the positions and widths of some low-lying resonance states with good accuracy. The perturbation approach yields zeroth-order energies and corrections in terms of the relevant quantum numbers. It thus allows a direct assignment of the energy levels without any reference to the corresponding eigenfunctions. The weak couplings between the high- and low-frequency motions can easily be treated by the same perturbative approach and numerically exact energies can finally be obtained. Copyright 2000 Academic Press.