Detection of the triplet HC4N radical by Fourier transform microwave spectroscopy

The triplet HC₄N radical in a linear carbon-chain form has been detected by Fourier transform microwave spectroscopy for the first time. Rotational transitions with fine and hyperfine structures, about 130 lines in total, were observed in a pulsed-discharge-nozzle supersonic expansion of the HC₃N sample diluted in Ar buffer gas. The spectrum was assigned to the linear HC₄N radical by various combinations of discharge gases, by the rotational, fine and hyperfine structures, and most decisively, by comparison of the determined molecular constants with those of the HCCN radical.     

Two-dimensional chirped-pulse Fourier transform microwave spectroscopy

Two-dimensional (2D) correlation techniques are developed for chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The broadband nature of the spectrometer coupled with fast digital electronics permits the generation of arbitrary pulse sequences and simultaneous detection of the 8-18 GHz region of the microwave spectrum. This significantly increases the number of rotation transitions that can be simultaneously probed, as well as the bandwidth in both frequency dimensions. We theoretically and experimentally evaluate coherence transfer of three- and four-level systems to relate the method with previous studies. We then extend the principles of single-quantum and autocorrelation to incorporate broadband excitation and detection. Global connectivity of the rotational energy level structure is demonstrated through the transfer of multiple coherences in a single 2D experiment. Additionally, open-system effects are observed from irradiating many-level systems. Quadrature detection in the indirectly measured frequency dimension and phase cycling are also adapted for 2D CP-FTMW spectroscopy.     

Chirped-pulse Fourier transform microwave spectroscopy of perfluoroiodoethane

The pure rotational spectrum of perfluoroiodoethane between 8.0 and 11.9 GHz has been measured on a search accelerated, correct intensity Fourier transform microwave (SACI-FTMW) spectrometer. The spectra is dense with 247 measured transitions in the given region. Only the anti conformer was observed for which rotational constants are reported. Nuclear electric quadrupole coupling constants due to the iodine-127 were determined and are reported. Also, two dipole forbidden/quadrupole allowed ΔJ=2 transitions were observed in the spectra. The observation of these transitions has been rationalized on the basis of near degeneracies between energy levels connected by χ_ab.     

Fourier transform microwave spectroscopy of the isocyanomethyl radical, CH(2)NC

The pure rotational spectrum of the isocyanomethyl radical, CH(2)NC, was measured for the first time by using a Fourier transform microwave spectrometer. The molecule was produced by a discharge of isocyanomethane, CH(3)NC, diluted in Ar or Ne. The spectral lines due to the N=1-0 and 2-1 transitions were recorded near 22 and 44 GHz, respectively. The observed spectrum showed a complicated fine and hyperfine structure because of the same order of interaction energies. Among the 39 spectral lines detected and assigned, the transitions with K(a)=1 show no hyperfine splitting due to the hydrogen nuclei, suggesting planarity for the molecule. Molecular constants such as rotational and spin-rotational parameters including centrifugal effects and hyperfine coupling constants due to both the nitrogen and the hydrogen nuclei were accurately determined. The structure and the astronomical implications of the molecule are discussed.     

Fourier transform ion cyclotron resonance spectroscopy

An ion cyclotron resonance (ICR) absorption spectrum has been obtained by exciting an ICR spectral segment with a fixed-frequency electric field pulse, followed by broad-band detection, digitization of the (time-domain) transient response, and digital Fourier transformation to produce the (frequency-domain) absorption spectrum. For a given signal-to-noise ratio and resolution, the FT-ICR method generates a spectrum in a time which is two orders of magnitude shorter than that required in conventional slow-sweep ICR detection. In the present example, a signal-to-noise ratio of 8:1 and a mass resolution of about 0.005 amu for CH₄⁺ (from CH₄ at a pressure of 8 X 10^?7 torr) have been achieved, using a single data acquisition period of 25.6 msec.     

Fourier transform microwave and millimeter wave spectroscopy of quinazoline, quinoxaline, and phthalazine

The pure rotational spectra of the bicyclic aromatic nitrogen heterocycle molecules, quinazoline, quinoxaline, and phthalazine, have been recorded and assigned in the region 13-87 GHz. An analysis, guided by ab initio molecular orbital predictions, of frequency-scanned Stark modulated, jet-cooled millimeter wave absorption spectra (48-87 GHz) yielded a preliminary set of rotational and centrifugal distortion constants. Subsequent spectral analysis at higher resolution was carried out with Fourier transform microwave (FT-MW) spectroscopy (13-18 GHz) of a supersonic rotationally cold molecular beam. The high spectral resolution of the FT-MW instrument provided an improved set of rotational and centrifugal distortion constants together with nitrogen quadrupole coupling constants for all three species. Density functional theory calculations at the B3LYP∕6-311+G?? level of theory closely predict rotational constants and are useful in predicting quadrupole coupling constants and dipole moments for such species.     

Hyperfine resolved spectrum of the bromomethyl radical, CH2Br, by Fourier transform microwave spectroscopy

Pure rotational spectra of the bromomethyl radical, CH(2)Br, were measured by using a Fourier transform microwave (FT-MW) spectrometer in order to fully resolve hyperfine structures arising from both the bromine and hydrogen nuclei. We detected a total of 124 lines for the (79)Br and (81)Br isotopomers, including K(a)=0 (ortho species) and K(a)=1 (para species). No hyperfine splitting due to the hydrogen nuclei was observed for the para species, directly confirming the planarity of the radical. We conducted a global analysis of our present FT-MW results and previous measurements in the millimeter-wave region and obtained an exhaustive list of molecular constants. The sign of the Fermi constant of the bromine nucleus was unambiguously determined to be positive, which is opposite to that found in previous work in the millimeter-wave region and in electron spin resonance experiment on this radical. The present study permitted a systematic comparison to be made of the hyperfine coupling constants of both the halogen and hydrogen nuclei for CH(2)X-type compounds, where X=F, Cl, and Br.     

The trans-isomer of formanilide studied by microwave Fourier transform spectroscopy

The rotational spectra of the trans-isomer of formanilide was recorded by microwave Fourier transform spectroscopy. The rotational and centrifugal distorsion constants as well as the quadrupole coupling constants have been accurately determined. It is shown that the stable conformation corresponds to a planar structure. The energy barrier between this conformation and the less stable one (the amino group lies in a plane perpendicular to the phenyl ring) has been evaluated by ab initio calculations.     

Fourier transform microwave spectroscopy of vinyldiacetylene, vinyltriacetylene, and vinylcyanodiacetylene

The rotational spectra of the three carbon chain molecules vinyldiacetylene (hex-1-ene-3,5-diyne, C(6)H(4)), vinyltriacetylene (oct-1-ene-3,5,7-triyne, C8H4), and its cyano analog vinylcyanodiacetylene (1-cyanohex-5-ene-1,3-diyne, C7H3N) have been observed for the first time by Fourier transform microwave spectroscopy of a supersonic molecular beam. The molecules were observed as products of an electrical discharge through selected precursor mixtures: ethylene/diacetylene and vinylacetylene/diacetylene for the pure hydrocarbon molecules and vinylacetylene/cyanoacetylene for vinylcyanodiacetylene. The measurements yield precise sets of rotational constants that compare very well with theoretical constants obtained by quantum chemical calculations at the B3LYP/cc-pVTZ level of theory. Since these three carbon chains are similar in structure and composition to known astronomical molecules and because of their significant polarity, all three are candidates for radio astronomical detection.     

Fourier transform ion cyclotron resonance detection of multiphoton ionization spectroscopy

Fourier transform ion cyclotron resonance (FT-ICR) detection was tested for resonanceenhanced multiphoton ionization (REMPI) spectroscopy. The (2+1) REMPI spectra of acetaldehyde were obtained in the wavelength range 364–354 nm via a two-photon resonant 3s ← n Rydberg transition. The space-charge effects on the REMPI spectra were examined in the vicinity of the 0 ₀ ⁰ transition. The trapping efficiency measurement shows that all the ions produced from REMPI dissociation processes are arrested in the ion cyclotron resonance cell even in the presence of space-charge interactions. Axial kinetic energy release distributions of ions were extracted from the trapping efficiency data obtained under a new space-charge-free condition. FT-ICR peak heights were measured as a function of pressure at different laser powers, magnetic field strengths, and ion excitation methods to test for the detection linearity. The FT-ICR detection responds linearly to the number of ions in a low pressure limit. The product branching ratio was measured by using various ion excitation methods and was compared with the previous quadrupole mass spectrometric study. FT-ICR detection yields the mass-selected REMPI spectra and the product branching ratio in the absence of kinetic shifts.     

Determination of structural parameters for ferrocenecarboxaldehyde using Fourier transform microwave spectroscopy

Gas-phase structural parameters for ferrocenecarboxaldehyde have been determined using Fourier transform microwave spectroscopy. Rotational transitions due to a-, b-, and c-type dipole moments were measured. Eighteen rotational constants were determined by fitting the measured transitions of various isotopomers using a rigid rotor Hamiltonian with centrifugal distortion constants. Least-squares fit and Kraitchman analyses have been used to determine the gas-phase structural parameters and the atomic coordinates of the molecule using the rotational constants for various isotopomers. Structural parameters determined from the least-squares fit are the Fe-C bond lengths to the cyclopentadienyl rings, r(Fe-C)=2.047(4) A, and the distance between the carbon atoms of the cyclopentadienyl rings, r(C-C)=1.430(2) A and r(C1-C1')=1.46(1) A of ring carbon and aldehyde carbon atom. Structural parameters were also obtained using density-functional theory calculations, and these were quite helpful in resolving ambiguities in the structural fit analysis, and providing some fixed parameters for the structural analysis. The results of the least squares and the calculations indicate that the carbon atoms of the Cp groups for ferrocenecarboxaldehyde are in an eclipsed conformation in the ground vibrational state.     

Conformational study of 2-phenylethylamine by molecular-beam Fourier transform microwave spectroscopy

The conformational preferences of the simplest amine neurotransmitter 2-phenylethylamine have been investigated using molecular beam Fourier transform microwave (MB-FTMW) spectroscopy. Two new conformers have been observed together with the two previously reported by Godfrey et al. [J. Am. Chem. Soc., 1995, 117, 8204]. The (14)N nuclear quadrupole hyperfine structure has been resolved for all four conformers. Comparison of the experimental rotational and quadrupole coupling constants with those calculated theoretically provides a conclusive test for the identification of all conformers. The two most stable conformers present a gauche (folded) disposition of the alkyl-amine chain and are stabilised by a weak NH...pi interaction between the amino group and the aromatic ring. The other two conformers show an anti (extended) arrangement of the alkyl-amine chain. Tunnelling splittings have been observed in the spectrum of one of the anti conformers. The post expansion relative abundances in the supersonic jet have been also investigated and related to the conformer energies.     

Probing thymine with laser ablation molecular beam Fourier transform microwave spectroscopy

Laser ablation in combination with molecular beam Fourier transform microwave spectroscopy has been used to establish unambiguously the presence of the diketo form of thymine in the gas phase and to obtain its structure.     

Some consequences of the Fourier transform in Fourier transform Raman spectroscopy

This paper reviews some of the differences between dispersive and Fourier transform (FT) Raman spectroscopy with the goal of highlighting some of the advantages and disadvantages of FT-Raman spectroscopy. In particular, the use of filters, Connes advantage, trading rules and the size of the multiplex and throughput advantages are discussed.     

Dispersive Fourier transform spectroscopy

A review is presented of recent developments in the methods of dispersive Fourier transform spectroscopy that have demonstrated the unique value of this broad band method for determining the optical constants of gases, liquids and solids.     

Fourier transform millimeter-wave spectroscopy of the ethyl radical in the electronic ground state

The pure rotational spectrum of the ethyl radical (C2H5) has been detected for the first time with the Fourier transform millimeter-wave spectrometer. The ethyl radical is produced by discharging the C2H5I gas diluted in Ar. The 1(01)-0(00) rotational transition of the ethyl radical is observed in the frequency range from 43,680 to 43,780 MHz. The observed spectrum shows a very complicated pattern of the fine and hyperfine structures of a doublet radical with the nuclear spins of five protons. The fine and hyperfine components are assigned with the aid of measurements of the Zeeman splittings. As a result, the 22 lines are ascribed to the transitions in the ground vibronic state (A2"). The rotational constant, the spin-rotation interaction constant, and hyperfine interaction constants are determined by the least-squares fit. The Fermi contact term of the alpha-proton is determined to be -64.1654 MHz in the gas phase, indicating that the structure of the -CH2 is essentially planar. The present rotational spectroscopic study further supports that the methyl group of the ethyl radical can be regarded as a nearly free internal rotor with a low energy barrier. A few unassigned lines still remain, which may be vibrational satellites of the internal rotation mode.     

Fourier transform Raman spectroscopy

The basic experimental aspects of Fourier transform Raman Spectroscopy are reviewed with an emphasis on detector technology. The sensitivity is comparable to dispersive Raman Spectroscopy using visible lasers. The ease of spectral subtraction is demonstrated and examples are given showing the elimination of fluorescence.     

Bolometric Fourier transform spectroscopy

Two examples are given of the results which can be obtained by use of bolometric techniques to measure very high far-infrared reflectivities from small single crystals at low temperatures. Both a simple and a composite bolometric technique are described.     

Zeeman-modulation Fourier transform spectroscopy

Low resolution Zeeman-modulation Fourier transform spectroscopy is demonstrated. The signal is produced by applying a magnetic field to the sample which must be paramagnetic. It is a convenient way to selectively detect unstable molecules. This source modulation new technique is not, as was first expected, requiring high resolution capabilities. Indeed the detection may be possible through the overall variation of the absorption of the line, induced by the magnetic field.