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.     

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.     

Frictionless mirror drive for intermediate resolution infrared Fourier transform spectroscopy

A simple and compact parallelogram mirror drive based on flexure pivots suitable for intermediate resolution Fourier transform spectroscopy is presented. The system permits 12 mm of mirror translation with a residual tilt of less than ±0.4 mrad in the horizontal plane and ±0.2 mrad in the vertical plane. A system prototype was built and fully characterized for a Fourier transform spectrometer operating on a stratospheric balloon.     

Chirped pulse Fourier transform microwave spectroscopy of 1,1,2,2-tetrafluoro-3-iodopropane

The pure rotational spectra of the two lowest energy conformers of 1,1,2,2-tetrafluoro-3-iodopropane have been investigated between the frequency limits of 7.5 and 16 GHz using chirped pulse Fourier transform microwave spectroscopy. Quantum chemical calculations have been performed to aid the spectral analyses. For the trans–trans conformer, which is calculated to be the lowest in energy, a total of 135 transitions were recorded. For the gauche–gauche conformer a total of 286 transitions were recorded. In both cases the complete iodine nuclear quadrupole coupling tensor has been determined.     

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 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.     

Microcomputers in Fourier transform spectroscopy

With the rapid advancement of VLSI technologies, microcomputer systems with relatively fast CPU processing time and electronic memory (RAM) of 1 Mbyte are now available at a reasonably low cost. We discuss the interfacing of microcomputers with 6502, 8086 and 68000 CPU to an FTS system. The performance of some A/D converters and microcomputer-controlled micropositioners available commercially are also discussed.     

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.     

Infrared Fourier transform spectroscopy of PH

The infrared vibration-rotation spectrum of the PH radical was observed in emission using a high-resolution Fourier transform spectrometer. The observation of five bands (1-0, 2-1, 3-2, 4-3, and 5-4) allowed the first six vibrational energy levels of the ground X³Σ⁻ state to be characterized. An RKR potential curve for the ground state was computed.     

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.     

基于傅里叶变换光谱技术的Zoom-FFT算法研究

在分析经典的Zoom-FFT算法基础上,提出一种基于傅里叶变换光谱技术的Zoom-FFT算法,用matlab仿真常规FFT算法和Zoom-FFT算法,对不同采样步长的干涉条纹进行数据处理,通过反演出的光谱曲线图和原始光谱曲线图可以看出:采样步长小于20 m时,FFT和Zoom-FFT算法都可以反演出光谱;而当采样步长大于20 m且小于33.3 m时,FFT算法未能反演出光谱,而Zoom-FFT算法仍然可以反演出光谱。     

Double-beam weighting in Fourier transform spectroscopy

This paper describes a double-beam weighting system in slow-scanning Fourier transform spectroscopy by use of a photo-conductive detector with fast response. It uses the method of amplitude modulation. The intensity of reference beam (A) and that of sample beam (B) are obtained by summing and subtracting the signals (A + B) and (A ? B), which are obtained in this form from a modulated signal by means of an electronic system. Merits arising from using a detector with fast response in double-beam weighting are also discussed. The operational performance of the system has been evaluated and it has been found that the spectra thus obtained are reproducible because they are kept within 3% bound and each measured value coincides with the averaged trace of single-beam measurements within ±2%.     

Femtosecond laser Fourier transform absorption spectroscopy

A femtosecond mode-locked laser is used for what is believed to be the first time as a broadband infrared source for high-resolution Fourier transform absorption spectroscopy. A demonstration is made with a Cr(4+):YAG laser. The entire nu(1)+nu(3) vibration-rotation band region of acetylene, observed after passing through a single-pass 80-cm-long cell, is simultaneously recorded between 1480 and 1600 nm, in 7.9 s with a signal-to-noise ratio equal to 1000. Two hot bands of the most abundant acetylene isotopologue and the nu(1)+nu(3) band of the (13)C(12)CH(2) are also present. Replacement of the usual conventional tungsten lamp by the bright laser source reduces by about a factor of 150 the recording time needed to get similar results. The noise equivalent absorption coefficient at 1 s averaging is equal to 7x10(-7) cm(-1)Hz(-1/2) per spectral element.     

Fourier transform microwave spectrum of the CO-dimethyl sulfide complex

The rotational spectrum of the CO-dimethyl sulfide (DMS) complex was measured in the frequency region from 4.8 up to 25 GHz by Fourier transform microwave spectroscopy. For the normal species 27 a-type and 57 c-type transitions were observed, while 16 and 8 c-type transitions were assigned for the species with ³⁴S and ¹³C in the DMS moiety, respectively, in natural abundance. In addition, 7 a-type and 48 c-type transitions were assigned for the complex with the ¹³CO enriched species as a component and 9 a-type and 42 c-type transitions for the complex with enriched C¹⁸O. No splitting was observed, which could be ascribed to the tunneling motion of the CO between two possible potential minima around DMS, while many transitions were split by the internal-rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to the methyl internal-rotation splitting, forbidden transitions were observed which apparently followed b-type selection rules. All of the observed transition frequencies for the normal species were analyzed simultaneously using a two-top internal-rotation and rotation Hamiltonian. The potential barrier height V₃ to internal rotation of the methyl groups of the DMS was determined to be 745.5 (30) cm⁻¹. The transition frequencies observed for all the isotopomers were analyzed using an asymmetric-rotor rotational Hamiltonian, to determine rotational and centrifugal distortion constants. The r_s coordinates calculated from the observed rotational constants led to the conclusion that the CO moiety was located in a plane perpendicular to the skeletal plane of the DMS and bisecting its CSC angle. This structure of the CO-DMS is very much different from that of the CO-DME, in which the CO is located in the DME skeletal plane. The distance between the centers of gravity of the two moieties, R_cm, was calculated to be 3.789 Å for the CO-DMS, which is longer by only 0.11 Å than that in the CO-DME complex: 3.68 Å, in spite of the fact that the van der Waals radius of the S atom is much larger than that of the O atom. The small difference in R_cm is, in part, ascribed to the location of the CO relative to the DMS/DME. The more important reason is that the intermolecular bonding of the CO-DMS is stronger than that of CO-DME; by assuming a Lennard-Jones-type potential, the force constant of the van der Waals stretching mode and the dissociation energy were estimated to be 2.7 Nm⁻¹ and 3.3 kJ mol⁻¹, respectively, which were larger than those of the CO-DME: 1.4 Nm⁻¹ and 1.6 kJ mol⁻¹.     

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.     

Pure rotational spectra of allene-1, 1-d2 and allene-d1 observed by microwave Fourier transform spectroscopy

Pure rotational transitions of allene-1, 1-d₂ and allene-d₁ in their vibronic ground state have been observed with a pulsed microwave Fourier transform spectrometer for the 8- to 18-GHz frequency range. Thirteen new transitions of allene-1, 1-d₂ with J up to 32 have been assigned. The measured transition frequencies have been combined with earlier measurements of Hirota and Matsumura [J. Chem. Phys. 59, 3038–3042 (1973)] in a least-squares fit of the rotational constants B and C and the centrifugal distortion constants Δ_J, Δ_JK, δ_J, and δ_K. Fifteen transition of allene-d₁ with J up to 34 have been assigned. The rotational constants A, B, and C, and the quartic centrifugal distortion constants Δ_J, Δ_JK, Δ_K, δ_J, and δ_K have been determined from the measured frequencies in a least-squares fit.     

Two-dimensional Fourier transform spectroscopy in the pump-probe geometry

Two-dimensional (2D) Fourier transform (FT) infrared spectroscopy is performed by using a collinear pulse-pair pump and probe geometry with conventional optics. Simultaneous collection of the third-order response and pulse-pair timing permit automated phasing and rapid acquisition of 2D absorptive spectra. To demonstrate the ability of this method to capture molecular dynamics, couplings and structure found in the conventional boxcar 2D FT spectroscopy, a series of 2D spectra of a metal carbonyl, and a beta-sheet protein are acquired.     

Imperfect optical figure in Fourier transform spectroscopy

An analytic model is presented for the spectral degradation introduced into Fourier transform spectroscopy by the presence of imperfect figure in the optics of a two beam interferometer. It allows tolerances to be defined for the figure of the optics if a required level of spectral performance is to be achieved. It confirms the validity of the practical rule-of-thumb that optical figures true to within a tenth of the shortest wavelength of interest will not degrade performance unacceptably.