The rotational spectrum of epifluorohydrin measured by chirped-pulse Fourier transform microwave spectroscopy

The rotational spectrum of epifluorohydrin measured by chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy is presented. A new CP-FTMW spectrometer capable of measuring the entire 7.5-18.5 GHz spectrum with a single polarizing pulse is described briefly. The CP-FTMW spectrometer takes advantage of recent advances in digital electronics by utilizing a 4.2 GS/s arbitrary waveform generator as a frequency source and a 12 GHz digital oscilloscope to digitize the down converted molecular free induction decay (FID). Signal averaging in the time domain is used to increase the signal-to-noise ratio. The rotational constants of three unique conformers of epifluorohydrin were measured, as well as the rotational constants of the three unique ¹³C isotopomers and the ¹⁸O isotopomer (in natural abundance) of the most stable conformer. The rotational constants of the two less stable conformers differ significantly from those previously reported [F.G. Fujiwara, J.L. Painter, H. Kim, J. Mol. Struct. 41 (1977) 169-175]. Ab initio calculations were performed for all three conformations and are compared to experimental values.     

Fourier transform microwave spectroscopy of aluminum hydrosulfide, AlSH

Pure rotational transitions of three isotopic species of aluminum hydrosulfide, AlSH, have been measured with a cavity pulsed jet Fourier transform microwave spectrometer. AlSH was prepared by the reaction of laser ablated Al metal with H₂S, and was stabilized in pulsed supersonic free jets of Ar. For each species the transition 1₀₁-0₀₀ was measured; hyperfine structure due to the nuclear spin of ²⁷Al was observed for the first time and analyzed. For Al³²SH and Al³²SD, the rotational constants are in excellent agreement with published values. For the third species, Al³⁴SH, this is the first observation, and its rotational constants are consistent with the published geometry. Information on the electronic structure of the molecule has been obtained using the ²⁷Al nuclear quadrupole coupling constants and nuclear spin-rotation constants. The latter have been used to evaluate ²⁷Al NMR shielding parameters, which are compared with those of other ²⁷Al compounds. These shieldings have been found to be in excellent agreement with theoretical predictions. The results should also help facilitate astrophysical searches for the molecule.     

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole

The room-temperature rotational spectrum of anisole from 8.7 to 18.3 GHz was collected with a waveguide-based chirped-pulse Fourier transform microwave spectrometer whose operating principles are described. Three spectra were assigned, corresponding to the vibrational ground state and the first and second excited states of the lowest frequency torsional mode. Results for the ground state and first excited state are in agreement with prior millimeter wave studies of this molecule. Microwave–microwave double resonance measurements also confirm these assignments.     

The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X Σ)

The pure rotational spectrum of HZnCl (X ¹Σ⁺) has been recorded using sub-millimeter direct-absorption methods in the range of 439–540 GHz and Fourier transform microwave (FTMW) techniques from 9 to 39 GHz. This species was produced by the reaction of zinc vapor and chlorine gas with H₂ or D₂ in a d.c. glow discharge for the sub-millimeter studies. In the FTMW measurements, HZnCl was created in a discharge nozzle from Cl₂ and (CH₃)₂Zn. Between 5 and 10 rotational transitions were measured in the sub-millimeter regime for four zinc and two chlorine isotopologues; four transitions were recorded with the FTMW machine for the main isotopologue, each consisting of several chlorine hyperfine components. The data are consistent with a linear molecule and a ¹Σ⁺ ground electronic state. Rotational and chlorine quadrupole constants were established from the spectra, as well as an r_m⁽²⁾ structure. The Zn–Cl and Zn–H bond lengths were determined to be 2.0829 and 1.5050 Å, respectively; in contrast, the Zn–Cl bond distance in ZnCl is 2.1300 Å, longer by 0.050 Å. The zinc–chlorine bond distance therefore shortens with the addition of the H atom. The ³⁵Cl electric quadrupole coupling constant of eQq = −27.429 MHz found for HZnCl suggests that this molecule is primarily an ionic species with some covalent character for the Zn–Cl bond.     

Rotational spectroscopy of the first excited state of the acetylenic C-H stretch of 3-fluoropropyne performed by infrared-Fourier transform microwave-microwave triple-resonance spectroscopy

The rotational spectra of 3-fluoropropyne in the ground and first excited acetylenic C-H stretch vibrational state have been measured. The pure rotational spectrum of the normal species and the ¹³C isotopomers were measured using FTMW-cwMW double-resonance spectroscopy based on the Autler-Townes (AC Stark) effect. The lineshape properties of this measurement make it possible to determine the transition strength, ΔJ-selection rules, and the relative energy ordering of the quantum states. The frequency accuracy of this technique is tested against a previous pure rotational study of 3-fluoropropyne. The rotational spectrum of vibrationally excited state was obtained through IR-FTMW-cwMW methods. In this technique a single-longitudinal-mode pulsed infrared laser source vibrationally excites the acetylenic C-H stretch with J-selectivity. The rotational spectrum of the excited state is then obtained by FTMW and FTMW-cwMW double-resonance methods. The excited-state measurements have a signal-to-noise ratio comparable to the pure rotational spectrum. The residuals in the excited-state fit are larger than those obtained in the ground-state fit. This greater deviation from a standard asymmetric top spectrum is most likely due to weak perturbations to the acetylenic C-H spectrum.     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

掺镱光纤放大器的啁啾脉冲失谐放大特性

研究了掺镱光纤放大器对中心频率为1 053nm的啁啾脉冲放大特性,发现针对高斯或超高斯脉冲,采用合适的带宽及入射光强能够使增益饱和和失谐放大相互消弱,从而得到一个良好的放大脉冲形状。计算了掺镱光纤放大器失谐放大带来的相位调制,发现对压缩质量影响较小。     

基于微波迈克耳孙干涉仪的傅里叶变换光谱分析实验

基于近代物理实验中微波的迈克耳孙干涉实验方法,在分析傅里叶变换光谱分析原理的基础上,利用微波分光仪首先分离了2个已知微波源的谱分布,并定量分析了最大分辨率与最大光程差、最大测量范围与采样间距之间的关系.     

Fourier transform microwave spectroscopy of N,N-dimethylacetamide

The jet-cooled Fourier-transform microwave spectrum of N,N-dimethylacetamide was recorded in the region of 12-24 GHz, and was analyzed to determine rotational constants and nuclear quadrupole coupling constants. Coriolis-like coupling parameters characterizing interaction between internal rotation of methyl groups and the overall rotation were also determined from internal-rotation tunneling splittings of the rotational transitions. The Coriolis-like coupling parameters permitted determination of the barrier heights to internal rotation of the three methyl groups, which were found to be 677, 237, and 183 cm⁻¹ for the C-methyl top, the trans-N-methyl top and the cis-N-methyl top, respectively.     

基于傅里叶变换模式的啁啾脉冲频域—时域相移转换的研究

基于频谱干涉原理和傅里叶变换的模式对啁啾脉冲频域相移转换为脉冲瞬态时域相移的基本原理进行了理论研究;推导出频域—时域相移转换过程中的相移误差传递公式;给出啁啾脉冲时域相移的最小时间分辨受制于参考脉冲的频谱宽度.对相移转换过程进行了数值模拟和分析,结果显示：通过该方法可以得到具有瞬态特性的时域相移,且频域相移误差是以被缩小的形式转换到时域的,与相移误差传递公式计算的结果具有较好的一致性. 关键词： 频谱干涉 频域相移 啁啾脉冲 时域相移     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy of N-methylpropionamide

In order to clarify the dynamical aspects of the peptide structure, N-methylpropionamide (NMPA) was investigated as an example of peptide molecules: XCONHY (X=CH₃CH₂ and Y=CH₃ for NMPA), paying special attention to the internal rotation of the two methyl groups. NMPA was found to have an almost planar skeleton with an extended syn/trans conformation, as indicated by the observed value of I_aa+I_bb−I_cc, and its rotational spectra were interpreted in terms of group G₁₈ consisting of six symmetry species: A₁, A₂, E₁, E₂, E₃, and E₄. The A₁ and E₂ spectra were observed split in most of b-type transitions, yielding the internal-rotation potential barrier V₃ of 796 (21) cm⁻¹ for CH₃ in the ethyl group referred to as C-CH₃. The spectra of the three E species: E₁, E₃, and E₄ appeared several tens to thousands MHz apart from the corresponding A₁ spectra, suggesting the internal-rotation potential barrier of CH₃ bonded to the nitrogen, called N-CH₃, to be quite low. In sharp contrast with the A₁ spectra, which were well fitted to the ordinary asymmetric-rotor spectral pattern, a few higher-order terms were required to reproduce the E₁ spectra, presumably because of the low N-CH₃ barrier. The spectral analysis thus performed, in fact, led to the V₃ of 80.06487 (14) cm⁻¹, an order of magnitude lower than that of C-CH₃. The E₃ and E₄ spectra were found to form triplets with the corresponding E₁ lines at the center, and the E₃-E₁ and E₄-E₁ splittings were explained essentially by the contributions of the C-CH₃ internal rotation combined with the kinetic-energy coupling between the two methyl groups. The torsion around the C-C bond between the ethyl and carbonyl groups was suggested by an ab initio calculation to be of double minimum nature, but the observed A₁ spectra did not show any indication of such a double-minimum potential for the C-C torsion, although the possibility of a small hump being present at a planar conformation could not be entirely eliminated. The present results on NMPA along with those obtained on other peptide molecules will be of some significance in clarifying important problems of structural biology such as protein folding and signal transfer through biological systems.     

Fourier transform microwave spectroscopy of LiCCH, NaCCH, and KCCH: Quadrupole hyperfine interactions in alkali monoacetylides

The alkali metal monoacetylides LiCCH, NaCCH, and KCCH and their deuterium isotopologues have been investigated using Fourier transform microwave (FTMW) spectroscopy in the frequency range 5-37 GHz. The molecules were synthesized in a supersonic expansion by the reaction of metal vapor, produced by laser ablation, with acetylene or DCCD. Use of target rods of the pure metal and a DC discharge immediately following the laser interaction region were significant factors in molecule production. Multiple rotational transitions were recorded for all species, except where only the J = 1 → 0 line was accessible (Li species). Quadrupole hyperfine interactions arising from the metal nuclei were resolved in each molecule, as well as those from the deuterium nucleus in the deuterated isotopologues. From a combined analysis with previous millimeter-wave data, refined rotational constants were determined for these species, as well as ⁷Li, ²³Na, ³⁹K, and D eQq parameters. The values of the metal quadrupole coupling constants are comparable to those of the alkali halides and hydroxides, indicating a similar degree of ionic character in the metal-ligand bond.     

Fourier transform spectroscopy of NbS

Emission bands attributed to the NbS radical have been observed in the near infrared and visible regions with FTS techniques using an electrodeless 2450 MHz discharge as a source. Transitions within the doublet and quartet manifolds were recorded at high resolution. The present paper gives the first rotational analysis of this molecule. Numerous bands within the doublet and quartet manifolds have been analyzed, resulting in the characterization of seven different electronic states, three in the doublet and four in the quartet manifold. The states have been labeled in analogy with NbO. The analyzed electronic states are: X⁴Σ⁻, C⁴Σ⁻, A′⁴Φ, D⁴Δ, a²Δ, c²Π, and e²Φ. Four additional substates in the doublet manifold have also been analyzed. In all, 27 vibrational sublevels have been included in the analysis, the total number of rotational lines being about 18 000. The positions of the analyzed transitions are: C⁴Σ⁻ → X⁴Σ⁻ near 15 670 cm⁻¹, D⁴Δ → A′⁴Φ near 7740 cm⁻¹, c²Π → a²Δ near 5850 cm⁻¹ and e²Φ → a²Δ near 8500 cm⁻¹. The overall picture is consistent with the corresponding analysis of NbO. However, three energy separations could not be derived from the experimental data in the case of NbS, i.e., the a²Δ− X⁴Σ⁻, A′⁴Φ− X⁴Σ⁻ and a²Δ_5/2-a²Δ_3/2 splittings. These were set to 4992, 5490, and 992 cm⁻¹, respectively, from preliminary ab initio calculations. In this way, a tentative energy level scheme could be drawn. The first order spin-orbit parameter of the A′⁴Φ state was indeterminable from the experimental data and was set to the value 170 cm⁻¹, derived from the same calculations.     

Fourier transform microwave spectroscopy of 1,1-dimethylsilacyclobutane. Interplay of two types of large-amplitude motions: two-top internal rotation and ring puckering

1,1-Dimethylsilacyclobutane, abbreviated as DMSCB, was investigated by Fourier transform microwave spectroscopy, by paying special attention to two types of large-amplitude motions in the molecule: two-top internal rotation and four-membered ring puckering and also to the coupling between the two. In order to clarify the unique feature of the internal dynamics in DMSCB in detail, two independent approaches were employed, one being a combination of a standard two-top theory of internal rotation and an established theory of ring puckering and the other a theory of large-amplitude motions developed by Hougen and his collaborators. In accordance with predictions by the two approaches based on symmetry consideration, the observed rotational spectra were found split into eight (or six when AE/EA lines were not resolved) components, which were assigned to the two-top states of AA, AE, EA, and EE symmetry, each being further split by puckering into two: the symmetric and antisymmetric states. The analyses by two approaches gave spectroscopic results, which were in good agreement with each other. The spectroscopic data on the normal species, combined with those on Si and C isotopic species, yielded molecular structure parameters including the puckering angle (the dihedral angle between the CSiC and CCC planes) of 28.64° or 30.26° (two possible sets). The splitting between the two lowest puckering states was determined to be 11.90(22) MHz, which led, with the equilibrium puckering angle, to the potential barrier to puckering of 395.3 or 347.0 cm⁻¹ for the two sets, respectively, which was slightly lower than the value 440 cm⁻¹ in a “parent” molecule: silacylcobutane. The first-order terms of the coupling between CH₃ internal rotation and overall rotation were converted to the barrier to internal rotation of 567.8 and 505.1 cm⁻¹ in the AE (two methyl groups rotating in the same direction, as viewed from Si) and EA (two methyl groups rotating in the opposite direction) states, respectively, which corresponded to the torsional frequencies of 154 and 144 cm⁻¹, at variance with the Raman data of 177 and 172 cm⁻¹, previously reported in literature.     

Laser and Fourier transform emission spectroscopy of TaCl

The emission spectrum of TaCl has been recorded at high resolution in the 3000-35 000 cm⁻¹ region using a Fourier transform spectrometer. The bands were observed by microwave excitation of a mixture of TaCl₅ vapor and 3.0 Torr of He. Several TaCl bands have also been recorded using the laser ablation/molecular beam source at the University of New Brunswick. A rotational analysis of a number of bands has been obtained and the majority of the stronger bands have been classified into three groups with different lower state spectroscopic constants. The three lower states have been identified as having Ω″ = 0⁺, Ω″ = 2, and (tentatively) Ω″ = 3. The Ω″ = 0⁺ and Ω″ = 2 states are very close in energy and one of these two states is the ground state of TaCl.     

脉冲宽度对PIN限幅器微波脉冲热效应的影响

通过数值求解半导体方程组仿真了高功率微波脉冲作用下的PIN二极管,研究了高功率微波脉冲的脉冲宽度对其烧毁的影响。发现脉冲宽度在ns至μs量级时,脉冲功率随脉冲宽度上升而下降,并且近似成反比。在此基础上,基于PIN二极管的Leenov模型和电路的戴维南定理对其机理进行了分析。在脉冲宽度由ns向μs量级变化中,器件热效应由绝热加热转为有热传导的加热;与此同时,其实际吸收功率由与入射功率成正比转为与入射功率开方成正比;此二者共同作用导致了脉冲宽度对烧毁影响。     

CMOS反相器内部瞬态闩锁效应的脉冲宽度效应理论模型

从基本半导体物理出发,通过求解载流子连续性方程,建立了能够定量描述引起CMOS反相器内部瞬态闩锁效应的微波脉冲功率阈值与脉冲宽度关系的解析理论模型。通过与仿真结果以及文献中实验数据的对比,验证了该理论模型的正确性。该理论模型表明,引起CMOS反相器内部瞬态闩锁效应的微波脉冲功率阈值首先随着脉冲宽度增加逐渐降低,但是存在一个明显拐点区域,当脉冲宽度超过该区域之后,引起闩锁效应的功率阈值变化不甚明显。     

能量倍增器法微波脉冲压缩

为了开展S波段能量倍增器脉冲压缩实验,对能量倍增器进行了冷测和热测工作,主要包括对能量倍增器的指标、参数的测量以及在高功率下对能量倍增器的输出功率、功率增益等参数的测量。实验中,完成了微波固态源系统的改造,研制了同步信号控制器,研究了输入输出脉冲宽度对输出峰值功率的影响,并对实验中可能的射频击穿问题进行了研究。在输入功率5 MW时,得到了功率增益7.122,输出脉宽260 ns,输出峰值功率35.35 MW。     

Rotational spectroscopy of iodobenzene and iodobenzene–neon with a direct digital 2–8 GHz chirped-pulse Fourier transform microwave spectrometer

The design of a chirped-pulse Fourier transform microwave spectrometer operating in the 2–8 GHz frequency range is presented. The linear frequency sweep is generated by an arbitrary waveform generator with a sampling rate of 20 GS/s. After amplification, the microwave pulse is broadcast into a vacuum chamber where it interacts with a supersonically expanded molecular sample. The resulting molecular free induction decay signal is amplified and digitized directly on a digital oscilloscope with a 20 GS/s sampling rate. No frequency mixing or multiplication is necessary in this spectrometer, which allows for very high pulse quality and phase stability. The performance of this spectrometer is demonstrated on the rotational spectrum of iodobenzene. All four distinct singly-substituted ¹³C isotopologues have been detected in natural abundance, as well as two isotopic species of a van der Waals cluster of iodobenzene with a neon atom. Spectroscopic constants and derived structural parameters for iodobenzene and for iodobenzene–Ne are reported. In addition, the use of microwave–microwave double-resonance experiments in this spectrometer to facilitate spectral assignments is presented.