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The carbazole moiety is a commonly identified structural motif in the high-molecular-weight components of petroleum, known as asphaltenes. Detailed characterization of carbazoles is important for understanding the structure of asphaltenes and addressing challenges in the areas of heavy oil recovery, transportation, upgrading, and oil spills, arising from asphaltene properties and composition. In this work we study carbazole and the four N-substituted carbazoles 9-methylcarbazole, 9-ethylcarbazole, 9-vinylcarbazole and 9-phenylcarbazole. Experimental far- and mid-infrared spectra of these five carbazoles are measured using transmission and photoacoustic techniques. The molecular structures of the monomers and the respective dimers, optimized at the ωB97X-D/6-311++G(d,p) level of the density functional theory (DFT), are subjected to harmonic vibrational frequency calculations. The effect of changing substituents on the N-H bond, π-π stacking distances, and angles between monomers within the dimers, in addition to intermolecular interactions, is investigated. Noncovalent interaction analysis is employed to highlight the areas of attractive and repulsive interactions in the dimers. Thermochemistry calculations show that the formation of dimers of all carbazoles is spontaneous at 298 K. Comparison of the calculated vibrational spectra of these compounds with experimental spectra indicates that the existence of both monomers and dimers must be invoked to account for the observed bands in the infrared spectra. Excellent correlations between the experimentally-determined and calculated harmonic vibrational energies are obtained, with an experimental-to-calculated scaling factor of 0.95-0.96. These findings highlight the coupled computational-experimental approach for the interpretation of vibrational spectra and are essential for improving the spectroscopic characterization of N-substituted carbazoles.

A discrepancy between theoretical and experimental values of the rotational barrier in benzaldehyde has been observed, which was attributed to inaccurate experimental results in part. Here, we report results on the -CHO torsion of benzaldehyde (C6H5CHO) based on a high resolution spectroscopic investigation in the far-infrared range in an effort to remove the experimental ambiguity. The rotationally-resolved vibrational spectra were measured with an unapodized resolution of 0.00064 cm-1 using synchrotron-based Fourier transform infrared (FTIR) spectroscopy at the Canadian Light Source. The torsional fundamental νt = 109.415429(20) cm-1 was unambiguously assigned via rovibrational analysis, followed by the tentative assignment of the first (2νt-νt) and second (3νt- 2νt) hot bands at 107.58 cm-1 and 105.61 cm-1, respectively, by comparison of the observed Q branch structures at high resolution with simulation based on a previous microwave study. This assignment is different from any previous low resolution infrared studies in which the intensity patterns were misleading. The key result of the assignment of the first three transitions allowed the determination of the barrier to internal rotation of (hc)1533.6 cm-1 (4.38 kcal mol-1). When compared with calculated results from vibrational second-order perturbation theory (VPT2) and the quasiadiabatic channel reaction path Hamiltonian (RPH) approach, the experimental value is still too low and this suggests that the discrepancy between theory and experiment remains despite the best experimental efforts.

The CSH-bending and CH3-rocking infrared bands of CH3SH have been investigated in Fourier transform spectra recorded at 0.001 cm−1 resolution employing synchrotron radiation at the Canadian Light Source in Saskatoon. The relative band strengths and structures are quite different from those of the CH3OH methanol analogue, with the CSH bend being very weak and both the in-plane and out-of-plane CH3 rocks being strong with intensities greater than the C–S stretch. The CSH bend has parallel a-type character with no detectable b-type component. The out-of-plane CH3 rock is a purely c-type perpendicular band, whereas the in-plane rock is of mixed a/b character. Sub-bands have been assigned for A and E torsional species up to about K = 10 for each vibrational mode, providing upper-state term values from which K-reduced substate origins were determined. For the CSH bend, the origins follow the customary oscillatory torsional pattern as a function of K with a sharply reduced amplitude of 0.362 cm−1 compared to the 0.653 cm−1 for the ground state. The torsional energy curves for the out-of-plane rock are also well-behaved but have inverted ordering of the A–E torsional splitting components and a larger amplitude of 1.33 cm−1. In contrast, the substate origins for the in-plane rock are scattered over a range of about 2 cm−1 without clear oscillatory structure. Several instances of coupling among the lower modes and the ground state via resonances between accidentally near-degenerate levels have been observed and characterized. Ab initio calculations are found to give a good representation of the frequency and relative intensity patterns for the lower vibrational modes.

Methyl formate (HCOOCH3) is an important interstellar molecule. More than 1000 rotational transitions including those from the ground state, torsionally excited states, and of its isotopologues have been observed towards several astrophysical sources. The laboratory spectra of methyl formate in the microwave spectral region contain many unassigned transitions and many of them are likely to be due to rotational transitions in the low-lying excited states. We report the laboratory identification of new rotational transitions in the COC deformation (ν12) excited state. The identification was made possible by combining the microwave data with rotation–vibration spectra taken in the far-infrared region at the Canadian Light Source synchrotron.

International audience; The high resolution far-infrared spectrum of trans-butadiene has been reinvestigated by Fourier-transform spectroscopy at two synchrotron radiation facilities, SOLEIL and the Canadian Light Source, at temperatures ranging from 50 to 340 K. Beyond the well-studied bands, two new fundamental bands lying below 1100 cm−1 , ν10 and ν24 , have been assigned using a combination of cross-correlation (ASAP software) and Loomis-Wood type (LWWa software) diagrams. While the ν24 analysis was rather straightforward, ν10 exhibits obvious signs of a strong perturbation, presumably owing to interaction with the dark ν9 + ν12 state. Effective rotational constants have been derived for both the v10 = 1 and v24 = 1 states. Since only one weak, infrared active fundamental band (ν23) of trans-butadiene remains to be observed at high resolution in the far-infrared, searches for the elusive gauche conformer can now be undertaken with considerably greater confidence in the dense ro-vibrational spectrum of the trans form.

The high resolution far-infrared spectrum of

This article describes transmission and photoacoustic spectroscopy experiments performed using coherent synchrotron radiation (CSR) at the Canadian Light Source. The storage ring was operated at energies of 1.0 and 1.5 GeV, with currents between 0.8 and 8.6 mA and synchrotron frequencies from 4.0 to 7.7 kHz. Relationships among these parameters and the associated energy curves were characterized in detail. Spectra of organosulphur and aromatic hydrocarbon compounds acquired using CSR exhibited absorption bands near 20 cm−1, likely due to translational and rotational motion in dimers. The location and extent of usable CSR can be modified through adjustment of the ring energy, synchrotron frequency, and ring current, making this radiation suitable for acquisition of spectra at very low wavenumbers.

Analysis of torsion-rotation structure in the far-infrared Fourier transform synchrotron spectrum of CH332SH recorded from 50 to 560 cm−1 at the Far-Infrared Beamline of the Canadian Light Source has been extended to higher near-free rotor torsional states reaching up into the region of the small-amplitude vibrations. A variety of sub-bands has been assigned for torsional quantum number up to vt = 5, expanding the database of ground-state energy term values to higher K and vt levels to provide a broad foundation for associated investigations of the vibrational spectrum. The origins of the high-vt sub-states fit quite well to a pattern of free-rotor parabolic curves as a function of K, but with a lower value of the torsional constant F than obtained from previous global analysis of lower-vt data. Numerous resonances perturbing and mixing coupled near-degenerate sub-states have been observed, arising from interactions both within the ground state and between ground and excited vibrational levels.

Pure CO2 spectra recorded at room temperature and different pressures (0.2–140 Torr) have been analyzed with the help of a fitting routine that takes into account asymmetries arising in the spectral lines due to pressure induced effects such as line mixing. The fitting procedure used in this study allows one to adjust the ro-vibrational constants for the band rather than fitting for individual line parameters. These constrained parameters greatly reduce the measurement uncertainties and allow us to observe the behavior of the weak lines corresponding to high J quantum numbers. We have also calculated line mixing parameters using approximations based on exponential nature of the energy difference between ground and upper vibrational states involved in the ro-vibrational band transitions. The calculated results show good agreement when compared with the experimentally determined parameters.

The infrared Fourier transform spectrum of the S–H stretching fundamental band of 12CH3 32SH has been recorded using synchrotron radiation at the far-infrared beamline of the Canadian Light Source ...

High-resolution Fourier transform spectra of the asymmetric methyl-bending and methyl-stretching bands of CH3SH have been recorded employing synchrotron radiation at the FIR beamline of the Canadian Light Source. Analysis of the torsion-rotation structure and relative intensities has revealed the novel feature that for both bend and stretch the in-plane and out-of-plane modes behave much like a Coriolis-coupled l-doublet pair originating from degenerate E modes of a symmetric top. As the axial angular momentum K increases, the energies of the coupled “l = ±1” modes diverge linearly, with effective Coriolis ζ constants typical for symmetric tops. For the methyl-stretching states, separated at K = 0 by only about 1 cm−1, the assigned sub-bands follow a symmetric top Δ(K − l) = 0 selection rule, with only ΔK = −1 transitions observed to the upper l = −1 in-plane A′ component and only ΔK = +1 transitions to the lower l = +1 out-of-plane A″ component. The K = 0 separation of the CH3-bending states is larger at 9.1 cm−1 with the l-ordering reversed. Here, both ΔK = +1 and ΔK = −1 transitions are seen for each l-component but with a large difference in relative intensity. Term values for the excited state levels have been fitted to J(J + 1) power-series expansions to obtain substate origins. These have then been fitted to a Fourier model to characterize the torsion-K-rotation energy patterns. For both pairs of vibrational states, the torsional energies display the customary oscillatory behaviour as a function of K and have inverted torsional splittings relative to the ground state. The spectra show numerous perturbations, indicating local resonances with the underlying bath of high torsional levels and vibrational combination and overtone states. The overall structure of the two pairs of bands represents a new regime in which the vibrational energy separations, torsional splittings and shifts due to molecular asymmetry are all of the same order, creating a challenging and complex vibration-torsion-rotation coupling environment.

In this work, very high-resolution far-infrared (FIR) and infrared (IR) Synchrotron Radiation spectra of C-13 substituted methanol species have been recorded with very high signal-to-noise (S/N) ratio in the entire region from 40 to 5000 cm−1. High resolution allowed the recording to be done with an unprecedented resolution of about 0.0014 cm−1 which is on the order of the doppler width of the lines. The peak of the spectral lines could be obtained with an estimated accuracy of ± 5 KHz. Analysis of the spectra has been performed for quantum numbers associated with the torsional ground state. Assignments have been obtained for K- values up to about 15 and J- values of about 35 for the three symmetry species. Asymmetry splitting has been observed for low K transitions and accurate asymmetry splitting constants have been obtained. Including the available microwave (MW) and millimeter-wave (MMW) measurements, a complete set of spectral line assignments have been obtained for the ground torsional state of the vibrational state. Following J.K. Watson’s method [1] all the spectral lines have been fitted to the exact term values of the energy levels. Localized perturbation has been observed for K = 9 A and state mixing resulted in forbidden transitions through intensity borrowing. A complete atlas has been presented for all possible quantum numbers for the ground state levels and the accurate term values have been obtained for all possible states. According to our knowledge, this atlas represents the most accurate line positions for this species reported so far. In addition, the results have been applied to confirm and obtain very accurate wavenumbers for several FIR laser lines pumped by CO2 lasers. The present atlas may be useful as a secondary wavenumber standard in the FIR region and should be useful for astrophysical detection.

Propene infrared absorption cross-sections are important for quantitative analysis of atmospheric spectra. Propene has been observed in Titan's atmosphere and may be detected in the atmospheres of giant planets. Infrared absorption cross-sections of propene (C3H6) have been measured in the 2680–3220 cm−1 region by high-resolution Fourier transform spectroscopy. Samples of propene were held at 202, 232, 265, 295 K with helium and nitrogen broadening gas pressures of 10, 30, 100 Torr. The cross section files are available for download.

In this work the high resolution synchrotron radiation Fourier transform spectrum in the range 1180–1300 cm−1 corresponding to the COH-bending vibrational mode has been recorded and analyzed. The spectrum shows a structure analogous to a parallel band. Since the COH bending motion is one of the main contributors to the asymmetry in the torsional hindering potential barrier, the torsional barrier height in the excited state is expected to be quite different from that of the ground state. This makes the spectrum to spread over a wide region. Although the spectrum corresponding to the P- and R-branch looks very complicated, the Q-branches are well resolved and can be identified without much difficulty. It was possible to assign the spectra for K = 0 to 10 for the trans- (e0) species. The interesting feature of the spectra is the absence of the lines for two other lower lying gauche symmetry species e1 and o1. The spectra due to any perpendicular transitions were absent as well. However some weak c-type transitions from gauche states (o1 and e1) in the ground state to the trans-species (e0) in the COD bending mode for low K-values ΔK = 0 have been seen to be present in the spectra. These along with similar transitions for the OCD vibrational band are under investigation and the results will be communicated elsewhere. In the present work, analysis of the spectrum has been carried out to obtain precise term values and molecular parameters in the excited COH-bending state for the trans-species. The results will be shown valuable to assign similar spectra for the methanol-D2. This work represents the first reported high resolution study of this illusive vibrational mode in methanol-D1.

Infrared absorption spectra for pure and He broadened propane have been recorded in the far-IR region (650-1300 cm −1 ) at the Canadian Light Source (CLS) facility using either the synchrotron or internal glowbar source depending on the required resolution. The measurements were made for 4 temperatures in the range 202–292 K and for 3 pressures of He broadening gas up to 100 Torr. Infrared absorption cross sections are derived from the spectra and the integrated cross sections are within 10 % of the corresponding values from the Pacific Northwest National Laboratory (PNNL) for all temperatures and pressures.

Fourier transform infrared absorption cross-sections of pure propane (C3H8) and propane broadened with H2 have been calculated from transmittance spectra recorded at temperatures from 292 K to 205 K. Transmittance spectra were recorded at the Canadian Light Source (CLS) Far-Infrared beamline, utilizing both the synchrotron source and the internal glowbar source. The absorption cross-sections have been calibrated to Pacific Northwest National Laboratory (PNNL) reference cross-sections of propane and can be used to interpret astronomical observations of giant planets such as Jupiter and Saturn as well as exoplanets.

An initial implementation of a tool for automatic assignment of spectra within the PGOPHER program is presented, together with its application to rotational analysis of the [small nu]11 band of cis-1,2-dichloroethene. It is based on the AUTOFIT algorithm presented by N. A. Seifert et al (J. Mol. Spectrosc., 2015, 312, 13) but implemented in a more efficient and general way, allowing it to be applied to a much wider variety of spectra.

Two new tools for computer assisted assignment of rotational spectra with the PGOPHER program are presented, aimed particularly at spectra where many individual lines are resolved. The first tool tries many different assignments, presenting a small number for possible refinement and a preliminary version of this has already been presented. The second tool, the nearest lines plot (a new style of residual plot) provides a clear indication as to whether a trial calculation is plausible, and allows rapid assignment of sets of related lines. It gives good results even for dense spectra with no obvious structure and in the presence of multiple interfering absorptions. The effectiveness of these tools is demonstrated by the analysis of high resolution IR spectra of 8 bands of cis- and trans-1,2-dichloroethene where, including hot bands and isotopologues, 31 vibrational transitions and 158 316 individual lines have been analysed, including perturbations for the higher energy states. Walkthroughs are presented to show this process is rapid.

The rotational spectrum of thiazole (c-C3H3NS, Cs, μa = 1.3 D, μb = 0.97 D) from 130 to 375 GHz and high-resolution infrared spectrum from 300 to 1300 cm−1 were obtained and analyzed. Nearly 4700 new, pure-rotational transitions were measured for the ground vibrational state, as well as over 1400 transitions for each of its three lowest-energy vibrationally excited states (ν18, ν17, and ν13). A total of over 5500 rotationally resolved, infrared transitions were measured for fundamentals ν17 and ν13, which form a Coriolis-coupled dyad. Transitions for each of these vibrational states of thiazole were fit to a sextic, A-reduced Hamiltonian in the Ir representation. Computed CCSD(T) values of the spectroscopic constants of thiazole show remarkable agreement with the experimentally determined values. Deuterium enrichment of thiazole allowed for the observation of the ground state and first fundamental (ν18) for three isotopic thiazoles. The direct impact on ν18 by isotopic substitution at C2 and C5 is observed. The combined rotational and high-resolution IR data allowed for an excellent fit of the Coriolis-coupled dyad of ν17 and ν13, which includes more than 60 nominal interstate transitions. Some of the measured resonant transitions are displaced by more than 30 GHz. The least-squares fit yielded six Coriolis coupling terms ( G a , G a J , G a K , G b , G b J , and G b K ) and very accurate measurements of the ν17 and ν13 band origins, 603.8511589 (17) cm−1 and 611.2214645 (18) cm−1, respectively. Collectively, these data provide reliable spectroscopic constants that can be used to predict the rotational spectra of thiazole up to 360 GHz.

Glycolaldehyde (GA) has been observed toward several different sources, with a broad range of rotational temperatures (8–300 K). At the high end, the temperature is comparable to the energy of the lowest vibrational states of GA, making the vibrational contribution to the partition function significant. Here, we report an analysis of the high-resolution far-infrared spectrum of GA, which features a plethora of well-resolved lines from 170–430 cm−1 (13–5 THz). We focus on the three fundamental vibrational bands in this range, i.e., the symmetric ν 12 bend at 282 cm−1, and the asymmetric ν 17 and ν 18 torsions at 360 and 208 cm−1, respectively. We assigned 23,266 transitions to 13,999 lines within these bands, which, when combined with the previously reported microwave and millimeter-wave spectra, allowed for refinement of the vibrationally excited rotational constants, and accurate determination of their band origins. Additionally, the assignment of a number of lines in several hot bands that are significantly populated at 300 K allowed for determination of their band origins. The rotational constants reported here should be useful in searches of vibrationally excited GA toward warm sources, and the accurately determined band origins allow for refinement of the vibrational partition function, and therefore column density, for a given excitation temperature.

Synchrotron radiation-based very high-resolution far-infrared (FIR) spectrum recorded at the Canadian Light Source (CSL) of doubly deuterated asymmetric methanol molecule (CHD2OH) have been analyzed for transitions associated with highly excited torsional-vibration–rotation levels. Complimentary millimeter-wave (MMW) transition frequencies have been measured using a backward wave oscillator based spectrometer at the Ohio State University. A new and simplified model has been proposed to treat the Hamiltonian Eigenvalues which do not require a large number of parameters with uncertain physical significance. A systematic approach has been laid out on how to proceed in order to obtain self-consistent and rigorously confirmed assignment of an extremely complicated spectrum arising due interaction with other states. New measurements in the MMW region should facilitate astrophysical determination of column densities of this abundant molecular species in cold interstellar clouds, especially in star-forming regions. The scarcity of MMW and the FIR laboratory database severely hindered the astrophysical work in the past. All the FIR assignments have been rigorously confirmed by closed combination relations (CR) using the MMW measurements and/or through ground state CRs from fundamental vibrational band analysis. These FIR transitions are presented in the form an atlas of about 900 lines. As a byproduct of the measurements, it was possible to put forward tentative assignments of optically pumped FIR laser lines.

In our effort to systematically study the far infrared (FIR) spectra of asymmetrically mono deuterated methanol (CH 2 DOH) and thereby obtain the transition wavenumbers with better and better accuracy (Mukhopadhyay, 2016a,b), the complete Fourier transform (FT) spectra from FIR to infrared (IR) vibrational bands (in the range 50–1190 cm −1 ) have been re-recorded using the Synchrotron Radiation Source at the Canadian Light Sources in Saskatchewan, Canada. The resolution of the spectrum is unprecedented, reaching beyond the Doppler limited resolution as low as about 0.0008 cm −1 with a signal to noise (S/N) ratio is many fold better than that can be obtained by commercially available FT spectrometer using thermal sources (e.g., Globar). Spectra were also recorded beyond 1190 cm −1 to about 5000 cm −1 at a somewhat lower resolution of 0.002–0.004 cm −1 . In this report the analysis of the b -type and c -type torsional - rotational spectra in the ground vibrational state corresponding to gauche- (e 1 /o 1 ) to gauche- (e 1 /o 1 ) and gauche- (e 1 /o 1 ) to trans- (e 0 ) states in the ground vibrational state are reported and an atlas of the wavenumber for about 2500 FIR assigned absorption lines has been prepared. The transitions within a given sub-band are analyzed using state dependent expansion parameters and the Q-branch origins. The data from previous results (Mukhopadhyay, 2016a,b) along with the present work allowed a global analysis yielding a complete set of molecular parameters. The state dependent molecular parameters reproduce the experimental wavenumbers within experimental uncertainty. In addition, the sensitivity of the spectrum allowed observation of forbidden transitions previously unobserved and helped reassignment of rotational angular momentum quantum numbers of some ΔK = ±1, Q-branch transitions in highly excited states recently reported in the literature. To our knowledge the wavenumbers reported in the present work are the most accurate so far reported in the literature and represent the highest resolution spectra for this molecular species.

The infrared absorption cross sections of ethane (C2H6) have been measured in the 3.3 µm region by high resolution Fourier transform spectroscopy. The ethane samples had temperatures of 203, 233, 263, 295 K with broadening gas pressures of 10 Torr, 30 Torr and 100 Torr of hydrogen or helium. These cross sections are useful for the interpretation of spectra of the giant planets.

Infrared absorption spectra of neopentane, 2,2-dimethylpropane, C(CH3)4, were recorded in the 2550-3350 cm-1 region by high resolution Fourier transform spectroscopy at the Canadian Light Source (CLS). Absorption cross sections were obtained for pure samples and with nitrogen as a broadening gas for 4 temperatures (202, 232, 265, 297 K).

High resolution infrared absorption cross sections of isobutane, (CH3)3CH, were measured in the 1050–1900 cm−1 spectral range by Fourier transform spectroscopy. Four sample temperatures (210, 234, 265 and 296 K) were used with three pressures (10, 30 and 100 Torr) of N2 and H2 broadening gas. Spectra of pure isobutane samples were also recorded. These cross sections are useful for the interpretation of infrared spectra of the Giant Planets and Titan. The isobutane cross sections give an upper limit of 3.91e-8 for its fractional abundance on Titan based on CIRS/Cassini infrared spectra. Using n-butane, CH3(CH2)2CH3, cross sections from the literature, we obtain an upper limit of 5.13e-7 for its abundance on Titan. The combined upper limit for both isomers of butane, C4H10, on Titan of 5.52e-7 is consistent with the lower limit of recent model predictions.

This paper presents the first high resolution (Δν = 0.00096 cm−1) IR investigation of 2–13C-propane. Spectra of the ν9(A1) CCC skeletal bending mode near 336.767 cm−1 (a b-type band) and the ν26(B2) methylene (CH2) rocking mode near 746.614 cm−1 (a c-type band) were recorded at the Canadian Light Source (CLS) synchrotron. The spectra were assigned both traditionally and with the aid of the pgopher program. As only limited microwave data are available for this molecule the present data was used to determine a new set of ground state constants that included centrifugal distortion terms. Upper state constants for both bands have been determined that provide a good simulation of the spectra. The analysis also included the strong a-type Coriolis resonance between the ν26 and 2ν9 states that causes strong perturbation-allowed transitions to appear in the spectrum. Lines of the 2ν9-ν9 hot band were also assigned and included in our analysis of the bending region. This data will be useful in identifying isotopic propane lines in Titan and other astrophysical objects.