M. Goubet

The far infrared spectrum of naphthalene characterized by high resolution synchrotron FTIR spectroscopy and anharmonic DFT calculations

Using synchrotron radiation, we performed the rotationally resolved Fourier transform infrared absorption spectroscopy of three bands of naphthalene C10H8, namely ν(46)-0 (centered at 782 cm(-1), 12.7 μm), ν(47)-0 (centered at 474 cm(-1), 21 μm), and ν(48)-0 (centered at 167 cm(-1), 60 μm). The intense CH bending out of plane ν(46)-0 band was recorded under supersonic jet-cooled conditions using a molecular beam (the Jet-AILES apparatus) and the low frequency ν(47)-0 and ν(48)-0 bands were measured at room temperature in a long absorption path cell. The simultaneous rotational analysis of these bands permitted us to refine the ground state (GS) and ν(46) rotational spectroscopic constants and to provide the first sets of constants for the ν(47) and ν(48) modes. The experimental rotational constants were then used as reference data to calibrate theoretical models in order to provide new insights into the accuracy of anharmonic calculations. The B97-1 functional associated with the cc-pVTZ and ANO-RCC basis sets gave a consistent set of results, for rotational constants and fundamental frequencies. The data presented here pave the way for the search of naphthalene through its far-infrared spectrum in different objects of the interstellar medium.

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.

Standard free energy of the equilibrium between the trans-monomer and the cyclic-dimer of acetic acid in the gas phase from infrared spectroscopy.

Survey jet-cooled spectra of acetic acid have been recorded in the infrared region (200-4000 cm(-1)) over a wide range of expansion conditions. From the variations of the relative intensities of the signals, vibrational transitions have been assigned unambiguously to the trans-monomer and cyclic-dimer. The IR-active fundamental frequencies have been determined at the instrumental accuracy of 0.5 cm(-1). This analysis of the jet-cooled spectra supported by electronic structure calculations permitted us to characterize the trans-monomer/cyclic-dimer equilibrium. From static cell spectra at 298 K, variations of the molar fractions ratio as a function of the total pressure were used to estimate the equilibrium constant and the Gibbs free energy of dimerization at 298 K. The very good agreement with the literature data shows that the present method is able to produce, from a single study, a free energy value as reliable as the one obtained from a large collection of data. In addition, the semi-empirical free energy value was used to estimate the accuracy of electronic structure calculations and in turn the accuracy of the derived useful information such as the dissociation energy of the complex (i.e. the strength of the hydrogen bonds) or the relative energies within the conformational landscape.

The cyclic ground state structure of the HF trimer revealed by far infrared jet-cooled Fourier transform spectroscopy

The rovibrationally resolved Fourier transform (FT) far infrared (FIR) spectra of two intermolecular librations of (HF)3, namely the in-plane ν6 and out-of-plane ν4 bending fundamentals centered, respectively, at about 494 cm(-1) and 602 cm(-1), have been recorded for the first time under jet-cooled conditions using the supersonic jet of the Jet-AILES apparatus. The simultaneous rotational analysis of 245 infrared transitions belonging to both bands enabled us to determine the ground state (GS), ν6 and ν4 rotational and centrifugal distortion constants. These results provided definite experimental answers to the structure of such a weakly bound trimer: firstly the vibrationally averaged planarity of cyclic (HF)3, also supported by the very small value of the inertia defect obtained in the GS, secondly the slight weakening of the hydrogen bond in the intermolecular excited states evidenced from the center of mass separations of the HF constituents determined in the ground, ν6 = 1 and ν4 = 1 states of (HF)3 as well as the decrease of the fitted rotational constants upon excitation. Finally, lower bounds of about 2 ns on ν6 and ν4 state lifetimes could be derived from the deconvolution of experimental linewidths. Such long lifetimes highlight the interest in probing low frequency intermolecular motions of molecular complexes to get rid of constraints related to the vibrational dynamics of coupled anharmonic vibrations at higher energy, resulting in loss of rotational information.

High resolution measurements supported by electronic structure calculations of two naphthalene derivatives: [1,5]- and [1,6]-naphthyridine—Estimation of the zero point inertial defect for planar polycyclic aromatic compounds

Polycyclic aromatic hydrocarbons (PAHs) molecules are suspected to be present in the interstellar medium and to participate to the broad and unresolved emissions features, the so-called unidentified infrared bands. In the laboratory, very few studies report the rotationally resolved structure of such important class of molecules. In the present work, both experimental and theoretical approaches provide the first accurate determination of the rotational energy levels of two diazanaphthalene: [1,5]- and [1,6]-naphthyridine. [1,6]-naphthyridine has been studied at high resolution, in the microwave (MW) region using a Fourier transform microwave spectrometer and in the far-infrared (FIR) region using synchrotron-based Fourier transform spectroscopy. The very accurate set of ground state (GS) constants deduced from the analysis of the MW spectrum allowed the analysis of the most intense modes in the FIR (ν38-GS centered at about 483 cm(-1) and ν34-GS centered at about 842 cm(-1)). In contrast with [1,6]-naphthyridine, pure rotation spectroscopy of [1,5]-naphthyridine cannot be performed for symmetry reasons so the combined study of the two intense FIR modes (ν22-GS centered at about 166 cm(-1) and ν18-GS centered at about 818 cm(-1)) provided the GS and the excited states constants. Although the analysis of the very dense rotational patterns for such large molecules remains very challenging, relatively accurate anharmonic density functional theory calculations appeared as a highly relevant supporting tool to the analysis for both molecules. In addition, the good agreement between the experimental and calculated infrared spectrum shows that the present theoretical approach should provide useful data for the astrophysical models. Moreover, inertial defects calculated in the GS (ΔGS) of both molecules exhibit slightly negative values as previously observed for planar species of this molecular family. We adjusted the semi-empirical relations to estimate the zero-point inertial defect (Δ0) of polycyclic aromatic molecules and confirmed the contribution of low frequency out-of-plane vibrational modes to the GS inertial defects of PAHs, which is indeed a key parameter to validate the analysis of such large molecules.

Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species

Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution study of the three lowest vibrational states of quinoline C9H7N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν45 and ν44 vibrational modes (located at about 168 cm(-1) and 178 cm(-1), respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations.

High-resolution spectroscopy and analysis of the V2 + V3 combination band of SF6 in a supersonic jet expansion

Sulphur hexafluoride is a very strong greenhouse gas whose concentration is increasing in the atmosphere. It is detected through infrared absorption spectroscopy in the strong ν3 fundamental region. Due to the existence of low-lying vibrational states of this molecule, however, many hot bands arise at room temperature and those are still not known. We present here a contribution to the elucidation of this hot band structure, by analysing the ν2 + ν3 combination band. We use a supersonic jet expansion high-resolution spectrum at a rotational temperature of ca. 25 K that was recorded thanks to the Jet-AILES setup at the Source Optimisée de Lumière d’Energie Intermédiaire du LURE (SOLEIL) Synchrotron. The simplified structure of this cold spectrum allowed us to assign 444 rovibrational lines and to fit effective Hamiltonian parameters, leading to a very satisfactory spectrum simulation. The parameters obtained in this way allow to calculate the spectrum of the ν3+ν2−ν2 hot band.

Towards the Detection of Explosive Taggants: Microwave and Millimetre-Wave Gas-Phase Spectroscopies of 3-Nitrotoluene

The monitoring of gas-phase mononitrotoluenes is crucial for defence, civil security and environmental interests because they are used as taggant for TNT detection and in the manufacturing of industrial compounds such as dyestuffs. In this study, we have succeeded to measure and analyse at high-resolution a room temperature rotationally resolved millimetre-wave spectrum of meta-nitrotoluene (3-NT). Experimental and theoretical difficulties have been overcome, in particular, those related to the low vapour pressure of 3-NT and to the presence of a CH3 internal rotation in an almost free rotation regime (V3 =6.7659(24)u2005cm-1 ). Rotational spectra have been recorded in the microwave and millimetre-wave ranges using a supersonic jet Fourier Transform microwave spectrometer (Trot <10u2005K) and a millimetre-wave frequency multiplication chain (T=293u2005K), respectively. Spectral analysis of pure rotation lines in the vibrational ground state and in the first torsional excited state supported by quantum chemistry calculations permits the rotational energy of the molecule, the hyperfine structure due to the 14 N nucleus, and the internal rotation of the methyl group to be characterised. A line list is provided for future in situ detection.