Rotational spectra of rare isotopic species of bromofluoromethane: determination of the equilibrium structure from ab initio calculations and microwave spectroscopy

Guided by theoretical predictions, the rotational spectra of the mono- and bideuterated species of bromofluoromethane, CDH(79)BrF, CDH(81)BrF, CD(2) (79)BrF, and CD(2) (81)BrF, have been recorded for the first time. Assignment of a few hundred rotational transitions led to the accurate determination of the ground-state rotational constants, all of the quartic and most of the sextic centrifugal distortion constants, as well as the full bromine quadrupole-coupling tensor for both (79)Br and (81)Br, in good agreement with corresponding theoretical predictions based on high-level coupled-cluster calculations. The rotational spectra of the (13)C containing species (13)CH(2) (79)BrF and (13)CH(2) (81)BrF have been observed in natural abundance and have been assigned, thus allowing the determination of the rotational and centrifugal distortion constants as well as the bromine quadrupole-coupling tensor. Furthermore, empirical equilibrium structures have been obtained within a least-squares fit procedure using the available experimental ground-state rotational constants for various isotopic species. Vibrational effects have been accounted for in the analysis using vibration-rotation interaction constants derived from anharmonic force fields computed at the second-order Moller-Plesset perturbation theory as well as coupled-cluster (CC) levels. The empirical equilibrium geometries obtained in this way agree well with the corresponding theoretical predictions obtained from CC calculations [at the CCSD(T) level] after extrapolation to the complete basis set limit and inclusion of core-valence correlation corrections and relativistic effects.     

High-resolution FTIR, microwave, and ab initio investigations of CH2 79BrF: ground, v(5) = 1, and v(6) = 1, 2 state constants

A spectroscopic study of CH279BrF in the infrared and microwave regions has been carried out. The rovibrational spectrum of the nu5 fundamental interacting with 2nu6 has been investigated by high-resolution FTIR spectroscopy. Owing to the weakness of the 2nu6 band, the v6 = 2 state constants have been derived from v6 = 1. For this reason, the rotational spectra of the ground and v6 = 1 states have been observed by means of microwave spectroscopy. Highly accurate ab initio computations have also been performed at the CCSD(T) level of theory in order to support the experimental investigation. As far as the nu5 band is concerned, the analysis of the rovibrational structure led to the identification of more than 3000 transitions, allowing the determination of a set of spectroscopic parameters up to sextic distortion terms and pointing out first-order c-type Coriolis interaction with the v6 = 2 state. With regard to the pure rotational spectra measurements, the assignment of several DeltaJ = 0, +1 transitions allowed the determination of the rotational, all the quartic, and most of the sextic centrifugal distortion constants, as well as the full bromine quadrupole coupling tensor for both the ground and v6 = 1 states.     

Rotational and rovibrational spectroscopy of CH3NC of the ground and ν4 = 1 vibrational states

The parallel vibration-rotation band ν(4) of methyl isocyanide (CH(3)NC), with a band center at 944.9 cm(-1), was studied by FTIR spectroscopy between 890 and 980 cm(-1) in order to improve the ground-state rotational constants. Such improvement is essential for the scheduled studies of excited vibrational levels and their mutual anharmonic resonances occurring at higher values of the K rotational number. Ground-state combination differences generated from this band, spanning values of J/K from 0 to 85/13, were combined with rotational data from the literature and newly measured rotational transitions, extending the J/K range from 3/0 up to 31/14, and fitted simultaneously with a fully quantitative reproduction of the data. The infrared data of the ν(4) band were analyzed together with rotational data of the ν(4) = 1 level, spanning values of J/K from 4/0 to 14/12. The fit in the approximation of an isolated vibrational state, with the transitions perturbed by weak local resonances excluded, yields reproduction of the data within experimental uncertainties.     

CF3I分子ν4带高分辨激光光谱研究

CF_3I分子的转动常数很小, 其振动谱带的转动结构在一般分辨率的光谱中不能分辨。我们用分辨率达2×10~(-3) cm~(-1)的红外二极管激光光谱的方法观察到了ν_4带的近十个Q支, 和上千条~PP, ~RR线, 以及ν_4+ν_6←ν_6和ν4+ν_3←ν_3两个热带跃迁, 并归属了其中的一些谱线, 研究了ν_4带中可能存在的振转相互作用, 利用最小二乘法拟合, 得到了有关的分子常数。     

The (CH2)2O-H2O hydrogen bonded complex. Ab Initio calculations and Fourier transform infrared spectroscopy from neon matrix and a new supersonic jet experiment coupled to the infrared AILES beamline of synchrotron SOLEIL

A series of hydrogen bonded complexes involving oxirane and water molecules have been studied. In this paper we report on the vibrational study of the oxirane-water complex (CH(2))(2)O-H(2)O. Neon matrix experiments and ab initio anharmonic vibrational calculations have been performed, providing a consistent set of vibrational frequencies and anharmonic coupling constants. The implementation of a new large flow supersonic jet coupled to the Bruker IFS 125 HR spectrometer at the infrared AILES beamline of the French synchrotron SOLEIL (Jet-AILES) enabled us to record first jet-cooled Fourier transform infrared spectra of oxirane-water complexes at different resolutions down to 0.2 cm(-1). Rovibrational parameters and a lower bound of the predissociation lifetime of 25 ps for the v(OH)(b) = 1 state have been derived from the rovibrational analysis of the ν(OH)(b) band contour recorded at respective rotational temperatures of 12 K (Jet-AILES) and 35 K (LADIR jet).     

Laser-induced fluorescence and pure rotational spectroscopy of the CH2CHS (vinylthio) radical

Laser-induced fluorescence (LIF) excitation spectra of the B-X (2)A(") electronic transition of the CH(2)CHS radical, which is the sulfur analog of the vinoxy (CH(2)CHO) radical, were observed under room temperature and jet-cooled conditions. The LIF excitation spectra show very poor vibronic structures, since the fluorescence quantum yields of the upper vibronic levels are too small to detect fluorescence, except for the vibrationless level in the B state. A dispersed fluorescence spectrum of jet-cooled CH(2)CHS from the vibrationless level of the B state was also observed, and vibrational frequencies in the X state were determined. Precise rotational and spin-rotation constants in the ground vibronic level of the radical were determined from pure rotational spectroscopy using a Fourier-transform microwave (FTMW) spectrometer and a FTMW-millimeter wave double-resonance technique [Y. Sumiyoshi et al., J. Chem. Phys. 123, 054324 (2005)]. The rotationally resolved LIF excitation spectrum for the vibronic origin band of the jet-cooled CH(2)CHS radical was analyzed using the ground state molecular constants determined from pure rotational spectroscopy. Determined molecular constants for the upper and lower electronic states agree well with results of ab initio calculations.     

Millimeter wave spectrum of bromomethyl radical, CH2Br

The rotational spectra of the two isotopic species of the bromomethyl radical, CH2 79Br and CH2 81Br, have been observed in their ground electronic state 2B1 in the 180-470 GHz frequency region, corresponding to a-type transitions from N=8-7 to N=21-20. The radical was produced by hydrogen abstraction of methylbromide (CH3Br) either by chlorine or by fluorine atoms in a free space cell. Hyperfine structure due to the bromine nucleus has been resolved in the observed spectra, and the rotational constants as well as the fine and hyperfine interaction constants were accurately determined for both isotopomers. The inertial defect was determined to be 0.028 96(20) and 0.028 95(20) amu A(2), for CH2 79Br and CH2 81Br, respectively, suggesting a planar structure. By fixing the [angle]HCH bond angle at 124.5 degrees , an effective molecular structure can be derived as r0(CBr)=1.848 A and r0(CH)=1.084 A. A comparison of the molecular structure of various halogen-substituted methyl radicals with respect to the planarity of these radicals is discussed.     

The Fourier transform and diode laser spectrum of the ν2 band of diazomethane

The infrared spectrum of the ν₂ band (NN stretching) of gaseous diazomethane at 2100 cm^?1 has been measured by means of an interferometer and a tunable diode laser spectrometer. For the first time the rotational J and K_a structure of this A-type parallel band has been resolved. Since the spectrum was found to be perturbed it was not possible to fit the upper state levels to an overall hamiltonian. Nine subbands have been analysed with the support of millimeter wave data for the ground vibrational state. Term values for the ν₂ = 1 vibrational state with K_a up to 5 have been obtained and subband origins, effective rotational constants B and centrifugal distortion constants D and H were determined for each K_a substate.     

Time-resolved Fourier transform emission spectroscopy of He/CH4 in a positive column discharge

Time-resolved Fourier transform infrared emission spectroscopy was applied to the study of a pulsed discharge in a He/CH(4) mixture. The dynamics of the formation and decay of acetylene ν(3) (3289 cm(-1)), methane ν(3) (3019 cm(-1)) and ν(1) (2917 cm(-1)), the CH radical electronic ground state X(2)Π(r) (2309-2953 cm(-1)), C(2) Bernath electronic transition B(1)Δ(g)-A(1)Π(u) (3337-3606 cm(-1)), molecular hydrogen emission transitions 5g-4f and 2p-2s, atomic hydrogen, and atomic helium were monitored in the 1800-4000 cm(-1) region. The time profile of the rotational and vibrational temperature of the CH radical was obtained for a 30 μs time interval during and after the discharge pulse. A kinetic model was used for the study of the chemical dynamics of the formation and decay of the individual fragments. The results from the model were compared to the experimental emission spectra.     

Sub-Doppler infrared spectroscopy of CH2D radical in a slit supersonic jet: isotopic symmetry breaking in the CH stretching manifold

First high-resolution infrared absorption spectra in the fundamental symmetric/asymmetric CH stretching region of isotopically substituted methyl radical, CH(2)D, are reported and analyzed. These studies become feasible in the difference frequency spectrometer due to (i) high density radical generation via dissociative electron attachment to CH(2)DI in a discharge, (ii) low rotational temperatures (23 K) from supersonic cooling in a slit expansion, (iii) long absorption path length (64 cm) along the slit axes, and (iv) near shot noise limited absorption sensitivity (5 × 10(-7)/√(Hz)). The spectra are fully rovibrationally resolved and fit to an asymmetric top rotational Hamiltonian to yield rotational/centrifugal constants and vibrational band origins. In addition, the slit expansion collisionally quenches the transverse velocity distribution along the laser probe direction, yielding sub-Doppler resolution of spin-rotation structure and even partial resolution of nuclear hyperfine structure for each rovibrational line. Global least-squares fits to the line shapes provide additional information on spin-rotation and nuclear hyperfine constants, which complement and clarify previous FTIR studies [K. Kawaguchi, Can. J. Phys. 79, 449 (2001)] of CH(2)D in the out-of-plane bending region. Finally, analysis of the spectral data from the full isotopomeric CH(m)D(3-m) series based on harmonically coupled Morse oscillators establishes a predictive framework for describing the manifold of planar stretching vibrations in this fundamental combustion radical.     

Analysis of the rotational structure in the high-resolution infrared spectrum of trans-hexatriene-1-13C1: a semiexperimental equilibrium structure for the C6 backbone of trans-hexatriene

trans-Hexatriene-1-(13)C(1) (tHTE-1-(13)C(1)) has been synthesized, and its high-resolution (0.0015 cm(-1)) infrared spectrum has been recorded. The rotational structure in the C-type bands for ν(26) at 1011 cm(-1) and ν(30) at 894 cm(-1) has been analyzed. To the 1458 ground state combination differences from these bands, ground state rotational constants were fitted to a Watson-type Hamiltonian to give A(0) = 0.8728202(9), B(0) = 0.0435868(4), and C(0) = 0.0415314(2) cm(-1). Upper state rotational constants for the ν(30) band were also fitted. Predictions of the ground state rotational constants for tHTE-1-(13)C(1) from a B3LYP/cc-pVTZ model with scale factors based on the normal species were in excellent agreement with observations. Similar good agreement was found between predicted and observed ground state rotational constants for the three (13)C(1) isotopologues of cis-hexatriene, as determined from microwave spectroscopy. Equilibrium rotational constants for tHTE and its three (13)C(1) isotopologues, of which two were predicted, were used to find a semiexperimental equilibrium structure for the C(6) backbone of tHTE. This structure shows increased structural effects of π-electron delocalization in comparison with butadiene and some differences from the cis isomer of HTE. Structures predicted with the MP2/cc-pVTZ model are also compared.     

Low-energy vibrations of the group 10 metal monocarbonyl MCO (M = Ni, Pd, and Pt): rotational spectroscopy and force field analysis

The rotational spectra of NiCO and PdCO in the ground and ν(2) excited vibrational states were observed by employing a source-modulated microwave spectrometer. The NiCO and PdCO molecules were generated in a free space cell by the sputtering reaction of nickel and palladium sheets, respectively, lining the inner surface of a stainless steel cathode with a dc glow plasma of CO and Ar. The molecular constants of NiCO and PdCO were determined by least-squares analysis. By force field analysis for the molecular constants of not only NiCO and PdCO but also of PtCO as previously reported, the harmonic force constants were determined for these three group 10 metal monocarbonyls. The vibrational wavenumbers derived for the lower M-C stretching vibrations were in good agreement with those obtained from the IR spectra in noble gas matrices and those predicted by several quantum chemical calculations published in the past. The bending vibrational wavenumbers derived by the force field analysis were also consistent with most quantum chemical calculations previously reported, but showed systematic discrepancies from the matrix IR values by about 40 cm(-1), even after reassignment (ν(2) band → 2ν(2) band) of the matrix IR spectra of PdCO and PtCO.     

Rotationally resolved infrared spectroscopy of adamantane

We present the first rotationally resolved spectra of adamantane (C(10)H(16)) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm(-1)range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (T(d) point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν(30), ν(28), ν(27), ν(26), ν(25), ν(24), and ν(23). The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10(-3) cm(-1).     

The visible absorption spectrum of OBrO, investigated by Fourier transform spectroscopy

By the utilization of a new laboratory method to synthesize OBrO employing an electric discharge, the visible absorption spectrum of gaseous OBrO has been investigated. Absorption spectra of OBrO have been recorded at 298 K, using a continuous-scan Fourier transform spectrometer at a spectral resolution of 0.8 cm(-1). A detailed vibrational and rotational analysis of the observed transitions has been carried out. The FTS measurements provide experimental evidence that the visible absorption spectrum of OBrO results from the electronic transition C(2A2)-X(2B1). Vibrational constants have been determined for the C(2A2) state (omega(1) = 648.3 +/- 1.9 cm(-1) and omega 2 = 212.8 +/- 1.2 cm(-1)) and for the X(2B1) state (omega 1 = 804.1 +/- 0.8 cm(-1) and omega 2 = 312.2 +/- 0.5 cm(-1)). The vibrational bands (1,0,0), (2,0,0), and (1,1,0) show rotational structure, whereas the other observed bands are unstructured because of strong predissociation. Rotational constants have been determined experimentally for the upper electronic state C(2A2). By modeling the band contours, predissociation lifetimes have been estimated. Further, an estimate for the absorption cross-section of OBrO has been made by assessing the bromine budget within the gas mixture, and atmospheric lifetimes of OBrO have been calculated using a photochemical model.     

High-resolution infrared spectroscopy of jet-cooled vinyl radical: symmetric CH2 stretch excitation and tunneling dynamics

First high-resolution IR spectra of jet-cooled vinyl radical in the C-H stretch region are reported. Detailed spectral assignments and least squares fits to an A-reduction Watson asymmetric top Hamiltonian yield rotational constants and vibrational origins for three A-type bands, assigned to single quantum excitation of the symmetric CH(2) stretch. Two of the observed bands arise definitively from ground state vinyl radical, as rigorously confirmed by combination differences predicted from previous midinfrared CH(2) wagging studies of Kanamori et al. [J. Chem. Phys. 92, 197 (1990)] as well as millimeter wave rotation-tunneling studies of Tanaka et al. [J. Chem. Phys. 120, 3604 (2004)]. The two bands reflect transitions out of symmetric (0(+)) and antisymmetric (0(-)) tunneling levels of vinyl radical populated at 14 K slit-jet expansion temperatures. The band origins for the lower-lower (0(+)<--0(+)) and upper-upper (0(-)<--0(-)) transitions occur at 2901.8603(7) and 2901.9319(4) cm(-1), respectively, which indicates an increase in the tunneling splitting and therefore a decrease in the effective tunneling barrier upon CH(2) symmetric stretch excitation. The third A-type band with origin at 2897.2264(3) cm(-1) exhibits rotational constants quite close to (but at high-resolution distinguishable from) the vinyl radical ground state, consistent with a CH(2) symmetric stretch hot band built on one or more quanta of excitation in a low frequency vibration. The observed CH(2) symmetric stretch bands are in excellent agreement with anharmonically scaled high level density functional theory (DFT) calculations and redshifted considerably from previous low resolution assignments. Of particular dynamical interest, Boltzmann analysis indicates that the pair of 0(+) and 0(-) tunneling bands exhibits 1:1 nuclear spin statistics for K(a)=even:odd states. This differs from the expected 3:1 ratio for feasible exchange of the two methylenic H atoms but is consistent with a 4:4 ratio predicted for interchange between all three H atoms. This suggests the novel dynamical possibility of large amplitude "roaming" of all three H atoms in vinyl radical, promoted by high internal vibrational excitation arising from dissociative electron attachment in the discharge.     

Rovibrational and dynamical properties of the hydrogen bonded complex (CH2)2S-HF: a combined free jet, cell, and neon matrix-Fourier transform infrared study

Fourier transform infrared spectra of the nu(s) (HF stretching) band of the (CH(2))(2)S-HF complex have been recorded at 0.1-0.5 cm(-1) resolution in a cooled cell, in a supersonic jet expansion seeded with argon and in a neon matrix at 4.5 K. The combination of controlled temperature effects over a range of 40-250 K and a sophisticated band contour simulation program allows the separation of homogeneous and inhomogeneous contributions and reveals significant anharmonic couplings between intramolecular and intermolecular vibrational modes similar to our previous work on (CH(2))(2)S-DF. The sign of the coupling constants is consistent with the expected strengthening of the hydrogen bond upon vibrational excitation of HF which also explains the observed small variations of the geometrical parameters in the excited state. The analysis of sum and difference combination bands involving nu(s) provides accurate values of intermolecular harmonic frequencies and anharmonicities and a good estimate of the dissociation energy of the complex. Frequencies and coupling parameters derived from gas phase spectra compare well with results from neon matrix experiments. The effective linewidth provides a lower bound for the predissociation lifetime of 10 ps. The comparison between effective linewidths and vibrational densities of states for (CH(2))(2)S-HF and -DF complexes highlights the important role of intramolecular vibrational redistribution in the vibrational dynamics of medium strength hydrogen bonds.     

Spectroscopic investigation of fluoroiodomethane, CH2FI: Fourier-transform microwave and millimeter-/submillimeter-wave spectroscopy and quantum-chemical calculations

Guided by theoretical predictions, the rotational spectrum of fluoroiodomethane, CH(2)FI, has been recorded and assigned. Accurate values are reported for the ground-state rotational constants, all quartic, sextic, and two octic centrifugal-distortion constants. The hyperfine structure of the rotational spectrum was thoroughly investigated using a Fourier-transform microwave spectrometer and the Lamb-dip technique in the millimeter-/submillimeter-wave region, thus allowing the accurate determination of the complete iodine quadrupole-coupling tensor and of the diagonal elements of the iodine spin-rotation tensor. Relativistic effects turned out to be essential for the accurate theoretical prediction of the dipole moment and quadrupole-coupling constants and were accounted for by direct perturbation theory and a spin-free four-component treatment based on the Dirac-Coulomb Hamiltonian. The relativistic corrections to the dipole moment amount to up to 34% and to the iodine quadrupole-coupling tensor to about 15-16% of the total values.     

Rotationally resolved infrared spectroscopy of a jet-cooled phenyl radical in the gas phase

The first high-resolution IR spectra of a jet-cooled phenyl radical are reported, obtained via direct absorption laser spectroscopy in a slit-jet discharge supersonic expansion. The observed A-type band arises from fundamental excitation of the out-of-phase symmetric CH stretch mode (nu19) of b2 symmetry. Unambiguous spectral assignment of the rotational structure to the phenyl radical is facilitated by comparison with precision 2-line combination differences from Fourier transform microwave and direct absorption mm-wave measurements on the ground state [R. J. McMahon et al., Astrophys. J., 2003, 590, L61]. Least-squares fits to an asymmetric top Hamiltonian permit the upper-state rotational constants to be obtained. The corresponding gas-phase vibrational band origin at 3071.8904 (10) cm(-1) is in remarkably good agreement with previous matrix isolation studies [A. V. Friderichsen et al., J. Am. Chem. Soc., 2001, 123, 1977], and indicates only a relatively minor red shift (approximately 0.9 cm(-1)) between the gas and Ar matrix phase environment. Such studies offer considerable promise for further high resolution IR study of other aromatic radical species of particular relevance to combustion phenomena and interstellar chemistry.     

Infrared vacuum-ultraviolet laser pulsed field ionization-photoelectron study of CH3Br+ (X(2)E(3/2))

By preparing methyl bromide (CH3Br) in selected rotational levels of the CH3Br(X(1)A1; v1 = 1) state with infrared (IR) laser excitation prior to vacuum-ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) measurements, we have observed rotationally resolved photoionization transitions to the CH3Br(+)(X(2)E(3/2); v1(+) = 1) state, where v1 and v1(+) are the symmetric C-H stretching vibrational mode for the neutral and cation, respectively. The VUV-PFI-PE origin band for CH3Br(+)(X(2)E(3/2)) has also been measured. The simulation of these IR-VUV-PFI-PE and VUV-PFI-PE spectra have allowed the determination of the v1(+) vibrational frequency (2901.8 +/- 0.5 cm(-1)) and the ionization energies of the origin band (85 028.3 +/- 0.5 cm(-1)) and the v1(+) = 1 <-- v1 = 1 band (84 957.9 +/- 0.5 cm(-1)).     

Fluorescence excitation and emission spectroscopy of the A1A"<--X1A' system of CHBr

We report fluorescence excitation and emission spectra of CHBr in the 450-750 nm region. A total of 30 cold bands involving the pure bending levels 2(0)(n) with n=2-8 and combination bands 2(0)(n)3(0)(1)(n=1-8), 2(0) (n)3(0)(2)(n=1-6), 2(0)(n)3(0)(3)(n=1-2), 1(0)(1)2(0)(n)(n=5-7), 1(0)(1)2(0)(n)3(0)(1)(n=4-6), and 1(0)(1)2(0)(n)3(0)(2)(n=5) in the A (1)A(")<--X (1)A(') system were observed, in addition to a number of hot bands. The majority of these are reported and/or rotationally analyzed here for the first time. Spectra were measured under jet-cooled conditions using a pulsed discharge source, and rotational analysis yielded band origins and rotational constants for both bromine isotopomers (CH (79)Br,CH (81)Br). The derived A (1)A(") vibrational intervals are combined with results of [Yu et al. J. Chem. Phys. 115, 5433 (2001)] to derive barriers to linearity for the 2(n), 2(n)3(1), and 2(n)3(2) progressions. The A (1)A(") state C-H stretching frequency is determined here for the first time, and the observed nu(3) dependence of the (79)Br-(81)Br isotope splitting in the A(1)A(") state is in good agreement with theoretical expectations. Our dispersed fluorescence spectra probe the vibrational structure of the X(1)A(') state up to approximately 9000 cm(-1) above the vibrationless level; the total number of levels observed is more than twice that previously reported. As first reported by [Chen et al. J. Mol. Spectrosc. 209, 254 (2001)], these spectra reveal numerous perturbations due to spin-orbit interaction with the low-lying a(3)A(") state. The results of a Dunham expansion fit of the ground state vibrational term energies, and comparisons with previous experimental and theoretical studies, are reported. Our results lead to several revised assignments, including the X (1)A(') C-H stretching fundamental. Globally, the vibrational frequencies of X(1)A('), a(3)A("), and A(1)A(") are in excellent agreement with theoretical predictions.