The radiative efficiency and global warming potential of HCFC-132b.

Hydro-chloro-fluoro-carbons (HCFCs) are potent greenhouse gases which strongly absorb the infrared (IR) radiation within the 8 - 12 µm atmospheric windows. Despite international policies schedule their phasing out by 2020 for developed countries and 2030 globally, HCFC-132b (CH2ClCClF2) has been recently detected with significant atmospheric concentration. In this scenario, detailed climate metrics are of paramount importance for understanding the capacity of anthropogenic pollutants to contribute to global warming. In this work, the radiative efficiency (RE) of HCFC-132b is experimentally measured for the first time and used to determine its global warming potential (GWP) over 20-, 100- and 500-year time horizon. Vibrational- and rotational-spectroscopic properties of this molecule are first characterized by exploiting a synergism between Fourier-transform IR (FTIR) spectroscopy experiments and quantum chemical calculations. Equilibrium geometry, rotational parameters and vibrational properties predicted theoretically beyond the double-harmonic approximation, are employed to assist the vibrational assignment  of the experimental trace. Finally, FTIR spectra measured over a range of pressures are used to determine HCFC-132b absorption cross section spectrum from 150 to 3000 cm-1, from which istantaneous and effective REs are derived and, in turn, used for GWP evaluation.

In Vitro and In Silico Vibrational-Rotational Spectroscopic Characterization of the Next-Generation Refrigerant HFO-1123.

Very short-lived substances have recently been proposed as replacements for hydrofluorocarbons (HFCs), in turn being used in place of ozone-depleting substances, in refrigerant applications. In this respect, hydro-fluoro-olefins (HFOs) are attracting particular interest because, due to their reduced global warming potential, they are supposed to be environmentally friendlier. Notwithstanding this feature, they represent a new class of compounds whose spectroscopic properties and reactivity need to be characterized to allow their atmospheric monitoring and to understand their environmental fate. In the present work, the structural, vibrational, and ro-vibrational properties of trifluorothene (HFO-1123, F2C = CHF) are studied by state-of-the-art quantum chemical calculations. The equilibrium molecular structure has an expected error within 2 mÅ and 0.2° for bond lengths and angles, respectively. This represents the first step toward the computation of highly accurate rotational constants for both the ground and first excited fundamental vibrational levels, which reproduce the available experimental data well within 0.1%. Centrifugal distortion parameters and vibrational-rotational coupling terms are computed as well and used to solve some conflicting experimental results. Simulation of the vibrational transition frequencies and intensities beyond the double harmonic approximation and up to three quanta of vibrational excitation provides insights into the couplings ruling the vibrational dynamics and guides the characterization of the gas-phase infrared spectrum experimentally recorded in the range of 200-5000 cm-1. The full characterization of the IR features is completed with the experimental determination of the absorption cross sections over the 400-5000 cm-1 region from which the radiative forcing and global warming potential of HFO-1123 are derived.

The Spectroscopic Characterization of Halogenated Pollutants through the Interplay between Theory and Experiment: Application to R1122.

In the last decade, halogenated ethenes have seen an increasing interest for different applications; in particular, in refrigeration, air-conditioning and heat pumping. At the same time, their adverse effects as atmospheric pollutants require environmental monitoring, especially by remote sensing spectroscopic techniques. For this purpose, an accurate characterization of the spectroscopic fingerprint-in particular, those of relevance for rotational-vibrational spectroscopy-of the target molecules is strongly needed. This work provides an integrated computational-theoretical investigation on R1122 (2-Chloro-1,1-difluoro-ethylene, ClHC=CF2), a compound widely employed as a key intermediate in different chemical processes. State-of-the-art quantum chemical calculations relying on CCSD(T)-based composite schemes and hybrid CCSD(T)/DFT approaches are used to obtain an accurate prediction of the structural, rotational and vibrational spectroscopic properties. In addition, the equilibrium geometry is obtained by exploiting the semi-experimental method. The theoretical predictions are used to guide the analysis of the experimentally recorded gas-phase infrared spectrum, which is assigned in the 400-6500 cm-1 region. Furthermore, absorption cross sections are accurately determined over the same spectral range. Finally, by using the obtained spectroscopic data, a first estimate of the global warming potential of R1122 vibrational spectra is obtained.

Scalable Synthesis of Few-Layered 2D Tungsten Diselenide (2H-WSe2) Nanosheets Directly Grown on Tungsten (W) Foil Using Ambient-Pressure Chemical Vapor Deposition for Reversible Li-Ion Storage.

We report a facile two-furnace APCVD synthesis of 2H-WSe2. A systematic study of the process parameters is performed to show the formation of the phase-pure material. Extensive characterization of the bulk and exfoliated material confirm that 2H-WSe2 is layered (i.e., 2D). X-ray diffraction (XRD) confirms the phase, while high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) clarify the morphology of the material. Focused ion beam scanning electron microscopy (FIB-SEM) estimates the depth of the 2H-WSe2 formed on W foil to be around 5-8 µm, and Raman/UV-vis measurements prove the quality of the exfoliated 2H-WSe2. Studies on the redox processes of lithium-ion batteries (LiBs) show an increase in capacity up to 500 cycles. On prolonged cycling, the discharge capacity up to the 50th cycle at 250 mA/g of the material shows a stable value of 550 mAh/g. These observations indicate that exfoliated 2H-WSe2 has promising applications as an LiB electrode material.

Molecular synthons for accurate structural determinations: the equilibrium geometry of 1-chloro-1-fluoroethene.

The equilibrium structure for 1-chloro-1-fluoroethene is reported. The structure has been obtained by a least-squares fit procedure using the available experimental ground-state rotational constants of eight isotopologues. Vibrational effects have been removed from the rotational constants using the vibration-rotation interaction constants derived from computed quadratic and cubic force fields obtained with the required quantum chemical calculations carried out by using both coupled cluster and density functional theory. The semi-experimental geometry obtained in this way has been also compared with the corresponding theoretical predictions obtained at the CCSD(T) level after extrapolation to the complete basis set limit and inclusion of core-valence corrections. These results allow completion of the molecular geometries of the isomers of chlorofluoroethene in addition to the cis and trans forms of 1-chloro-2-fluoroethene already published.

Accurate Vibrational-Rotational Parameters and Infrared Intensities of 1-Bromo-1-fluoroethene: A Joint Experimental Analysis and Ab Initio Study.

The medium-resolution gas-phase infrared (IR) spectra of 1-bromo-1-fluoroethene (BrFC═CH2, 1,1-C2H2BrF) were investigated in the range 300-6500 cm-1, and the vibrational analysis led to the assignment of all fundamentals as well as many overtone and combination bands up to three quanta, thus giving an accurate description of its vibrational structure. Integrated band intensity data were determined with high precision from the measurements of their corresponding absorption cross sections. The vibrational analysis was supported by high-level ab initio investigations. CCSD(T) computations accounting for extrapolation to the complete basis set and core correlation effects were employed to accurately determine the molecular structure and harmonic force field. The latter was then coupled to B2PLYP and MP2 computations in order to account for mechanical and electrical anharmonicities. Second-order perturbative vibrational theory was then applied to the thus obtained hybrid force fields to support the experimental assignment of the IR spectra.

Study of the Vibrational Spectra and Absorption Cross Sections of 1-Chloro-1-fluoroethene by a Joint Experimental and Ab Initio Approach.

The gas-phase infrared spectra of 1-chloro-1-fluoroethene (geminal chloro-fluoroethene, ClFC═CH2, 1,1-C2H2ClF) were recorded at medium resolution in the range of 400-6400 cm-1, and the vibrational analysis led to revised assignments for the ν11 (A″ symmetry), ν2 (A' symmetry), and ν1 (A' symmetry) bands. Besides the fundamentals, all the most important spectral features were interpreted in terms of overtone and combination bands, thus obtaining an accurate description of the vibrational structure of ClFC═CH2. Accurate measurements of absorption cross-sectional spectra were carried out, and integrated band intensity data were determined. High-level ab initio calculations of harmonic and anharmonic force fields thoroughly supported and guided the analysis and the disentangling of the several strongly coupled polyads involving many vibrational levels. Diagonalization of the effective Hamiltonian with the off-diagonal elements involving several Fermi and Darling-Dennison resonance coefficients computed by the theoretical cubic and quartic force constants provided the predicted energy levels in good agreement with the vibrational assignments. The calculated infrared intensities, obtained by taking into account anharmonic corrections, were compared to the accurate experimental absorption cross-sectional data determined here.

The energetic of (CH2F2)2 investigated by TDL IR spectroscopy and DFT computations: From collision induced relaxation of ro-vibrational transitions to non-covalent interactions.

Difluoromethane (CH2F2) is an atmospheric pollutant presenting strong absorptions within the 8-12 µm atmospheric window, hence it can contribute to global warming. Its dimer, (CH2F2)2, is bound through weak hydrogen bonds (wHBs). Theoretically, wHBs are of paramount importance in biological systems, though their modeling at density functional theory (DFT) level requires dispersion correlations to be accounted for. In this work, the binding energy (3.1 ± 0.5 kcal mol(-1)) of (CH2F2)2 is experimentally derived from the foreign broadening coefficients of the monomer compound, collisionally perturbed by a range of damping gases. Measurements are carried out on CH2F2 ro-vibrational transitions by means of tunable diode laser spectroscopy. Six stationary points on the potential energy surface (PES) of the dimer are investigated at DFT level by using some of the last generation density functionals (DFs). The Minnesota M06 suite of functionals as well as range separated DFs and DFs augmented by the non-local (NL) van der Waals (vdW) dispersion corrections are considered. DFT results are compared to reference values at the estimated complete basis set (CBS) limit of CCSD(T) theory (coupled cluster with singles and doubles augmented by a perturbational estimate of connected triples) and to the experimental binding energy. The M06-2X, M06-HF, VV10, BLYP-NL, and B3LYP-NL DFs reproduce CCSD(T)/CBS binding energies with a mean absolute deviation <0.4 kcal mol(-1) and about the same deviation from the experimental value. The present results are of twofold relevance: (i) they show that binding energy of homodimers can be conveniently obtained from the monomer's foreign broadening coefficients and that the correct simulation of hydrogen bonds involved in (CH2F2)2 needs non-covalent interactions to be included into DFT; (ii) O2- and N2-pressure broadening parameters represent fundamental data for exploiting the efficacy of remote sensing measurements employed to retrieve temperature and concentration profiles of our atmosphere.

Insights into the interaction between CH2F2 and titanium dioxide: DRIFT spectroscopy and DFT analysis of the adsorption energetics.

Difluoromethane (CH2F2, HFC-32) has been proposed as a valid replacement for both CFCs and HCFCs (in particular HCFC-22), and nowadays it is widely used in refrigerant mixtures. Due to its commercial use, in the last years, the atmospheric concentration of HFC-32 has increased significantly. However, this molecule presents strong absorptions within the 8-12µm atmospheric window, and hence it is a greenhouse gas which contributes to global warming. Heterogeneous photocatalysis over TiO2 surface is an interesting technology for removing atmospheric pollutants since it leads to the decomposition of organic compounds into simpler molecules. In the present work, the adsorbate-substrate interaction between CH2F2 and TiO2 is investigated by coupling experimental measurements using DRIFT spectroscopy to first-principle simulations at DFT/B3LYP level. The experimental results confirm that CH2F2 interacts with the TiO2 surface (∼80% rutile, 20% anatase) through both F and H atoms and show that the DRIFT technique is well suited to study the adsorption of halogenated methanes over semiconductor surfaces. DFT calculations are carried out by considering different periodicities and surface coverages, according to a structure involving an acid-base interaction between the F and Ti(4+) atoms as well as an H-bond between the CH2 group and an O(2-) ion. Lateral effects and energetics are analyzed in the limit of low coverage according to a procedure taking into account the binding, interaction, and distortion energies. The simulation at the different surface coverages and periodicities suggests similar decomposition pathways for the different investigated ensemble configurations.

N2-, O2- and He-collision-induced broadening of sulfur dioxide ro-vibrational lines in the 9.2 µm atmospheric window.

Sulfur dioxide (SO2) is a molecule of considerable interest for both atmospheric chemistry and astrophysics. In the Earth's atmosphere, it enters in the sulfur cycle and it is ubiquitous present in polluted atmospheres, where it is responsible for acid rains. It is also of astrophysical and planetological importance, being present on Venus and in interstellar clouds. In this work the collisional broadening of a number of ν1 ro-vibrational lines of SO2 perturbed by N2, O2 and He are investigated at room temperature in the 9 µm atmospheric region by means of high resolution tunable diode laser (TDL) infrared spectroscopy. From N2- and O2-broadening coefficients, the broadening parameters of sulfur dioxide in air, useful for atmospheric applications, are derived as well. From the present measurements some conclusions on the quantum number dependence of the N2-, O2- and He-broadening coefficients are drawn. While the J dependence is weak for all the perturbers investigated, different trends with Ka are reported. N2-broadening coefficients show a slight decrease with increasing values of Ka, whereas O2 and He broadening cross sections first increase up to Ka(″)≈6 and then they keep a nearly constant value. A comparison and a brief discussion on the efficiency of self-, N2-, O2- and He-collisional dynamics are given. The data obtained represent a significant analysis on foreign broadening of SO2 useful for atmospheric remote sensing and astrophysical applications.

An integrated experimental and quantum-chemical investigation on the vibrational spectra of chlorofluoromethane.

The vibrational analysis of the gas-phase infrared spectra of chlorofluoromethane (CH2ClF, HCFC-31) was carried out in the range 200-6200 cm(-1). The assignment of the absorption features in terms of fundamental, overtone, combination, and hot bands was performed on the medium-resolution (up to 0.2 cm(-1)) Fourier transform infrared spectra. From the absorption cross section spectra accurate values of the integrated band intensities were derived and the global warming potential of this compound was estimated, thus obtaining values of 323, 83, and 42 on a 20-, 100-, and 500-year horizon, respectively. The set of spectroscopic parameters here presented provides the basic data to model the atmospheric behavior of this greenhouse gas. In addition, the obtained vibrational properties were used to benchmark the predictions of state-of-the-art quantum-chemical computational strategies. Extrapolated complete basis set limit values for the equilibrium geometry and harmonic force field were obtained at the coupled-cluster singles and doubles level of theory augmented by a perturbative treatment of triple excitations, CCSD(T), in conjunction with a hierarchical series of correlation-consistent basis sets (cc-pVnZ, with n = T, Q, and 5), taking also into account the core-valence correlation effects and the corrections due to diffuse (aug) functions. To obtain the cubic and quartic semi-diagonal force constants, calculations employing second-order Møller-Plesset perturbation (MP2) theory, the double-hybrid density functional B2PLYP as well as CCSD(T) were performed. For all anharmonic force fields the performances of two different perturbative approaches in computing the vibrational energy levels (i.e., the generalized second order vibrational treatment, GVPT2, and the recently proposed hybrid degeneracy corrected model, HDCPT2) were evaluated and the obtained results allowed us to validate the spectroscopic predictions yielded by the HDCPT2 approach. The predictions of the deperturbed second-order perturbation approach, DVPT2, applied to the computation of infrared intensities beyond the double-harmonic approximation were compared to the accurate experimental values here determined. Anharmonic DFT and MP2 corrections to CCSD(T) intensities led to a very good agreement with the absorption cross section measurements over the whole spectral range here analysed.

Anharmonic theoretical simulations of infrared spectra of halogenated organic compounds.

The recent implementation of the computation of infrared (IR) intensities beyond the double-harmonic approximation [J. Bloino and V. Barone, J. Chem. Phys. 136, 124108 (2012)] paved the route to routine calculations of infrared spectra for a wide set of molecular systems. Halogenated organic compounds represent an interesting class of molecules, from both an atmospheric and computational point of view, due to the peculiar chemical features related to the halogen atoms. In this work, we simulate the IR spectra of eight halogenated molecules (CH2F2, CHBrF2, CH2DBr, CF3Br, CH2CHF, CF2CFCl, cis-CHFCHBr, cis-CHFCHI), using two common hybrid and double-hybrid density functionals in conjunction with both double- and triple-ζ quality basis sets (SNSD and cc-pVTZ) as well as employing the coupled-cluster theory with basis sets of at least triple-ζ quality. Finally, we compare our results with available experimental spectra, with the aim of checking the accuracy and the performances of the computational approaches.

Anharmonic force field and vibrational dynamics of CH2F2 up to 5000 cm(-1) studied by Fourier transform infrared spectroscopy and state-of-the-art ab initio calculations.

Difluoromethane (CH(2)F(2), HFC-32) is a molecule used in refrigerant mixtures as a replacement of the more environmentally hazardous, ozone depleting, chlorofluorocarbons. On the other hand, presenting strong vibration-rotation bands in the 9 µm atmospheric window, it is a greenhouse gas which contributes to global warming. In the present work, the vibrational and ro-vibrational properties of CH(2)F(2), providing basic data for its atmospheric modeling, are studied in detail by coupling medium resolution Fourier transform infrared spectroscopy to high-level electronic structure ab initio calculations. Experimentally a full quantum assignment and accurate integrated absorption cross sections are obtained up to 5000 cm(-1). Ab initio calculations are carried out by using CCSD(T) theory and large basis sets of either the correlation consistent or atomic natural orbital hierarchies. By using vibrational perturbation theory to second order a complete set of vibrational and ro-vibrational parameters is derived from the ab initio quartic anharmonic force fields, which well compares with the spectroscopic constants retrieved experimentally. An excellent agreement between theory and experiment is achieved for vibrational energy levels and integrated absorption cross sections: transition frequencies up to four quanta of vibrational excitation are reproduced with a root mean square deviation (RMSD) of 7 cm(-1) while intensities are predicted within few km mol(-1) from the experiment. Basis set performances and core correlation effects are discussed throughout the paper. Particular attention is focused in the understanding of the anharmonic couplings which rule the vibrational dynamics of the |ν(1)>, |2ν(8)>, |2ν(2)> three levels interacting system. The reliability of the potential energy and dipole moment surfaces in reproducing the vibrational eigenvalues and intensities as well as in modeling the vibrational and ro-vibrational mixings over the whole 400-5000 cm(-1) region is also demonstrated by spectacular spectral simulations carried out by using the ro-vibrational Hamiltonian constants, and the relevant coupling terms, obtained from the perturbation treatment of the ab initio anharmonic force field. The present results suggest CH(2)F(2) as a prototype molecule to test ab initio calculations and theoretical models.

Toward a complete understanding of the vinyl fluoride spectrum in the atmospheric region.

A deep and comprehensive investigation of the vinyl fluoride (CH(2)CHF) spectrum in the atmospheric window around 8.7 µm is presented. At first, the ro-vibrational patterns are modelled to an effective Hamiltonian, which also takes into account the coupling of the C-F stretching vibration, ν(7), with the neighbouring vibrational combination ν(9)+ν(12). The obtained Hamiltonian gives very accurate simulations and predictions of the ro-vibrational quantum energies. Then, in the main part of the work, an experimental and theoretical study of vinyl fluoride self-broadening collisions is carried out for the first time. The broadening coefficients obtained experimentally are compared with those calculated by a semiclassical theory, demonstrating a significant contribution of collisional coupling effects between lines connecting pairs of degenerate (or nearly degenerate) rotational levels. Finally, the experimentally retrieved integrated absorption coefficients are used to calculate the absorption cross-section of the ν(7) normal mode, from which dipole transition moments are derived. The obtained results provide a deep insight into the spectral behaviour of vinyl fluoride, in a spectral region of primary relevance for atmospheric and environmental determinations. Indeed, the data presented constitute an accurate model for the remote sensing of vinyl fluoride--a molecule of proved industrial importance which can lead to hazardous effects in the atmosphere and affects human's health.

Microwave, high-resolution infrared, and quantum chemical investigations of CHBrF2: ground and v4 = 1 states.

A combined microwave, infrared, and computational investigation of CHBrF(2) is reported. For the vibrational ground state, measurements in the millimeter- and sub-millimeter-wave regions for CH(79)BrF(2) and CH(81)BrF(2) provided rotational and centrifugal-distortion constants up to the sextic terms as well as the hyperfine parameters (quadrupole-coupling and spin-rotation interaction constants) of the bromine nucleus. The determination of the latter was made possible by recording of spectra at sub-Doppler resolution, achieved by means of the Lamb-dip technique, and supporting the spectra analysis by high-level quantum chemical calculations at the coupled-cluster level. In this context, the importance of relativistic effects, which are of the order of 6.5% and included in the present work using second-order direct perturbation theory, needs to be emphasized for accurate predictions of the bromine quadrupole-coupling constants. The infrared measurements focused on the ν(4) fundamental band of CH(79)BrF(2). Fourier transform investigations using a synchrotron radiation source provided the necessary resolution for the observation and analysis of the rotational structure. The spectroscopic parameters of the v(4) = 1 state were found to be close to those of the vibrational ground state, indicating that the ν(4) band is essentially unaffected by perturbations.

Spectroscopic study of CHBrF(2) up to 9500 cm(-1): Vibrational analysis, integrated band intensities, and ab initio calculations.

The gas-phase infrared spectra of bromodifluoromethane, CHBrF(2), have been examined at medium resolution in the range of 200-9500 cm(-1). The assignment of the absorptions in terms of fundamental, overtone, combination, and hot bands, assisted by quantum chemical calculations is consistent all over the region investigated. Accurate values of integrated band intensities have also been determined for the first time in the range of 500-6000 cm(-1). Structural and molecular spectroscopic properties have been calculated at high level of theory. The coupled cluster CCSD(T) method in conjunction with a hierarchical series of correlation consistent basis sets has been employed and extrapolation to complete basis set has been considered for the equilibrium geometry. Vibrational analysis based on the second order perturbation theory has been carried out with the ab initio anharmonic force constants calculated using the second order Moller-Plesset perturbation as well as coupled cluster [CCSD(T)] theory. A good agreement between the computed and the experimental data also including the integrated infrared band intensities has been obtained.

Spectroscopic measurements of SO(2) line parameters in the 9.2 mum atmospheric region and theoretical determination of self-broadening coefficients.

Sulfur dioxide is still the subject of numerous spectroscopic studies since it plays an active role in the chemistry of Earth's atmosphere and it is a molecule of proven astrophysical importance. In the present work we have determined the self-broadening and integrated absorption coefficients for several lines in the nu(1) band spectral region around 9.2 mum. Besides the parameters of the lines belonging to the nu(1) fundamental of (32)SO(2), also those for some rovibrational lines of the nu(1)+nu(2)-nu(2) hot band of the (32)SO(2) isotopologue and the nu(1) band of the (34)SO(2) isotopic species have been determined. The measurements have been carried out at 297 K using a tunable diode laser spectrometer. The self-broadening parameters have also been theoretically determined employing a semiclassical formalism based on the Anderson-Tsao-Curnutte approximation. The study has been completed with the determination of the vibrational cross sections of the three fundamental bands measured from the spectra recorded at a resolution of 0.2 cm(-1) using a Fourier transform infrared spectrometer.

Infrared spectrum and anharmonic force field of CH2DBr.

The gas-phase infrared spectrum of monodeuteromethyl bromide, CH2DBr, has been examined at medium resolution in the range 400-10000 cm(-1), leading to the identification of 70 vibrational transitions. The assignment of the absorptions in terms of fundamentals, overtones, combinations, and hot bands, assisted by quantum chemical calculations, is consistent all over the region investigated. The (79/81)Br isotopic splitting for the lowest fundamental nu6 and the value for the v8 = 1 level have been now precisely determined. Anharmonic resonances are very marginal for all fundamentals and the Coriolis interaction effects are clearly evident in the nu4/nu8 band system, in the nu2 and nu7 fundamentals. Spectroscopic parameters, obtained from the analysis of partially resolved rotational structure, have been derived in the symmetric tops limit approximation. High-quality ab initio calculations have been performed, and harmonic and anharmonic force fields have been predicted from coupled cluster CCSD(T) calculations employing the cc-pVTZ basis set. A good agreement between computed and experimental data, also including the C-H stretching overtones at 6000 and 9000 cm(-1), has been obtained.

Infrared spectra, integrated band intensities, and anharmonic force field of H2C=CHF.

The gas-phase infrared spectra of vinyl fluoride, H(2)C=CHF, have been examined at medium resolution in the range 400-8000 cm(-1). The assignment of the absorptions in terms of fundamental, overtone, and combination bands, assisted by quantum chemical calculations, is consistent all over the region investigated. Spectroscopic parameters, obtained from the analysis of partially resolved rotational structure of some bands, have been derived and compared with the corresponding calculated values. Accurate values of integrated band intensities have also been determined for the first time. High-level ab initio calculations with large basis sets have been performed. Correlated harmonic force fields have been obtained from coupled cluster CCSD(T) calculations with the cc-pVQZ basis set, while anharmonic force constants have been computed employing the less resource demanding cc-pVTZ basis set. A good agreement between the computed and the experimental data has been obtained including those for the integrated infrared band intensities.

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.