Micro-solvation of CO in water: infrared spectra and structural calculations for (D2O)2-CO and (D2O)3-CO.

The weakly-bound molecular clusters (D2O)2-CO and (D2O)3-CO are observed in the C-O stretch fundamental region (≈2150 cm-1), and their rotationally-resolved infrared spectra yield precise rotational parameters. The corresponding H2O clusters are also observed, but their bands are broadened by predissociation, preventing detailed analysis. The rotational parameters are insufficient in themselves to determine cluster structures, so ab initio calculations are employed, and good agreement between the experiment and theory is found for the most stable cluster isomers, yielding the basic cluster geometries as well as confirming the assignments to (D2O)2-CO and (D2O)3-CO. The trimer, (D2O)2-CO, has a near-planar geometry with one D atom from each D2O slightly out of the plane. The tetramer, (D2O)3-CO, has the water molecules arranged in a cyclic quasi-planar ring similar to the water trimer, with the carbon monoxide located 'above' the ring and roughly parallel to its plane. The tunneling effects observed in the free water dimer and trimer are quenched by the presence of CO. The previously observed water-CO dimer together with the trimer and tetramer reported here represent the first three steps in the solvation of carbon monoxide.

Infrared bands of CS2 dimer and trimer at 4.5 µm.

We report observation of new infrared bands of (CS2)2 and (CS2)3 in the region of the CS2 ν1 + ν3 combination band (at 4.5 µm) using a quantum cascade laser. The complexes are formed in a pulsed supersonic slit-jet expansion of a gas mixture of carbon disulfide in helium. We have previously shown that the most stable isomer of (CS2)2 is a cross-shaped structure with D2d symmetry and that for (CS2)3 is a barrel-shaped structure with D3 symmetry. The dimer has one doubly degenerate infrared-active band in the ν1 + ν3 region of the CS2 monomer. This band is observed to have a rather small vibrational shift of -0.844 cm-1. We expect one parallel and one perpendicular infrared-active band for the trimer but observe two parallel bands and one perpendicular band. Much larger vibrational shifts of -8.953 cm-1 for the perpendicular band and -8.845 cm-1 and +16.681 cm-1 for the parallel bands are observed. Vibrational shifts and possible vibrational assignments, in the case of the parallel bands of the trimer, are discussed using group theoretical arguments.

Characterization of OCS-HCCCCH and N2O-HCCCCH Dimers: Theory and Experiment.

The infrared spectra of the weakly bound dimers OCS-HCCCCH, in the region of the ν1 fundamental band of OCS (2050 cm-1), and N2O-HCCCCH, in the region of the ν1 fundamental band of N2O (2200 cm-1), were observed in a pulsed supersonic slit jet expansion probed with tunable diode/QCL lasers. Both OCS-HCCCCH and N2O-HCCCCH were found to have planar structure with side-by-side monomer units having nearly parallel axes. These bands have hybrid rotational structure which allows for estimates of the orientation of OCS and N2O in the plane of their respective dimers. Analogous bands for OCS-DCCCCD and N2O-DCCCCD were also observed and found to be consistent with the normal isotopologues. Various levels of theoretical calculations were performed to find stationary points on the potential energy surface, optimized structures, and interaction energies. Four stable geometries were found for OCS-HCCCCH and three for N2O-HCCCCH. The rotational parameters at CCSD(T*)-F12c level of theory give results in very good agreement with those obtained from the observed spectra. In both dimers, the experimental structure corresponds to the lowest energy isomer.

Detection of a higher energy isomer of the CO-N2O van der Waals complex and determination of two of its intermolecular frequencies.

Infrared spectra in the carbon monoxide CO stretch region (∼2150 cm-1) and in the ν3 asymmetric stretch region of N2O (∼2223 cm-1) are assigned to the previously unobserved O-bonded form of the CO-N2O dimer ("isomer 2"). This van der Waals complex has a planar skewed T-shaped structure like that of the previously observed C-bonded form ("isomer 1"), but with the CO rotated by 180°. The effective intermolecular distance between the centers of mass is 3.51 Å for isomer 2 as compared to 3.88 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.502(5) cm-1 for the coupled disrotatory motion or the uncoupled CO rock and 21.219(5) cm-1 for the out-of-plane rock. We show that the published ab initio study on this system is inadequate in predicting the intermolecular frequencies for isomer 2 of CO-N2O.

New Infrared Bands of the C-Bonded Isomer of OC-N2O and Determination of Two Intermolecular Frequencies.

Three combination bands involving intermolecular modes of the most stable isomer of the OC-N2O van der Waals complex have been observed, two in the carbon monoxide CO stretch region (∼2150 cm-1) and one in the ν3 asymmetric stretch region of N2O (∼2223 cm-1). Vibrational assignment is achieved by comparison with data recently published ( Barclay , A. ; et al. Chem. Phys. Lett. 2016 , 62 , 651 ), concerning OC-CO2. Two of these bands involve the same intermolecular mode, one with the CO stretch and the other with the ν3 asymmetric stretch of N2O. The values of intermolecular frequency deduced from these two bands agree very well, showing no significant dependence on intramolecular vibrational excitation.

Discerning Inter- and Intramolecular Vibrations of Sulfur Polyaromatic Compounds.

Thiophenes are an important class of molecules in fields as diverse as petrochemistry, molecular electronics, and optoelectronics. Thiophenic submolecular motifs are thought to play a role in molecular association and nanoaggregation phenomena in both pure materials and natural and synthetic mixtures. Vibrational (infrared and Raman) spectroscopy provides the means to characterize these species. In this work far-infrared photoacoustic and low-frequency Raman spectra of a series of polycyclic aromatic hydrocarbons containing sulfur have been measured and interpreted using DFT calculations based on a perturbational-variational method coupled with potential truncation. The approach and outcomes illustrate how inter- and intramolecular vibrations for thiophenic systems in single and multicomponent mixtures can be discriminated. This work offers the perspective to search the inter- and intramolecular signatures of the main submolecular motifs and heteroelements postulated as being present in the asphaltenes.

Communication: Spectroscopic observation of the O-bonded T-shaped isomer of the CO-CO2 dimer and two of its intermolecular frequencies.

Infrared spectra in the carbon monoxide CO stretch region (≈2150 cm(-1)) are assigned to the previously unobserved O-bonded form of the CO2-CO dimer ("isomer 2"), which has a planar T-shaped structure like that of the previously observed C-bonded form ("isomer 1"), but with the CO rotated by 180°. The effective center of mass intermolecular distances are 3.58 Å for isomer 2 as compared to 3.91 Å for isomer 1. In addition to the fundamental band, two combination bands are observed for isomer 2, yielding values for two intermolecular vibrational modes: 14.19 cm(-1) for the in-plane CO bend and 22.68 cm(-1) for the out-of-plane bend.

New combination bands of N2O-CO2, N2O-OCS, and N2O-N2 complexes in the N2O ν(1) region.

Spectra of the weakly bound complexes N2O-CO2, N2O-OCS, and N2O-N2 were studied in the region of the ν1 fundamental of N2O (∼2224 cm(-1)) using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion with an effective rotational temperature of about 2.5 K. One new combination band was observed for each complex: a band involving an intermolecular in-plane bending mode for N2O-N2, a band involving the disrotation (in-plane geared bend) for of N2O-CO2, and a band involving the out-of-plane torsional vibration for isomer b of N2O-OCS. Small perturbations were noted for the N2O-OCS band. Because of the absence of theoretical prediction, the nature of the intermolecular bending mode for N2O-N2 has not been identified. The resulting intermolecular frequencies are 34.175(1), 17.107(1), and 22.334(1) cm(-1) for N2O-CO2, N2O-OCS, and N2O-N2, respectively. In addition, the previously known fundamental band of N2O-N2 at 2225.99 cm(-1) was analyzed in improved detail. This band exhibits very weak a-type transitions which were not detected in the first infrared observation of this complex, indicating that N2O-N2 is not exactly T-shaped. That is, the N2O molecular axis is not exactly perpendicular to the a-inertial axis, in agreement with a previous structural determination of this complex by rotational spectroscopy.

A new look at the infrared spectrum of the weakly bound CO-N2 complex.

A broad-band (2135-2165 cm(-1)) infrared spectrum of the CO-N2 van der Waals complex is obtained, using a tunable quantum cascade laser to probe a pulsed supersonic expansion from a slit jet source. Analysis of the spectrum results in the characterization of four new 'stacks' of rotational levels for CO-orthoN2 (all in the v(CO) = 1 upper state) and five new stacks for CO-paraN2 (three in the upper state and two in the vCO = 0 lower state). This considerably expands our knowledge of a rather fundamental weakly bound complex and should lead to improved determinations of the intermolecular forces governing interactions between the carbon monoxide and nitrogen molecules.

CO dimer: the infrared spectrum revisited.

A broad-band (2135-2200 cm(-1)) infrared spectrum of the CO dimer is recorded using a tunable quantum cascade laser to probe a supersonic jet expansion with an effective rotational temperature of about 2.5 K. Analysis of the spectrum reveals the first known levels of the excited state (vCO = 1) with A(+) symmetry and establishes that resonant vibrational splittings are small (<0.2 cm(-1)) for both the C-bonded and O-bonded dimer isomers. The spectrum extends over a surprisingly large range, with somewhat reduced intensity above 2150 cm(-1). A total of 28 new "stacks" of rotational levels having A(-) symmetry are assigned for vCO = 1 on the basis of combination differences, adding to the 8 stacks previously known, and extending up to 51 cm(-1) above the vCO = 1 origin. Assignments are given for the first 13 stacks of vCO = 1 in terms of the very low frequency geared bending intermolecular vibration.

Communication: Spectroscopic evidence for a planar cyclic CO trimer.

A high-resolution spectrum in the region of 2144 cm(-1) is assigned to the previously elusive CO trimer. In spite of interference from the CO dimer and some remaining unexplained details, there is strong evidence for a planar, cyclic, C-bonded trimer structure, with C(3h) symmetry and 4.42 Å intermolecular separation, in agreement with theoretical calculations. A modest vibrational blueshift of +0.85 cm(-1) is observed for the CO trimer, as compared to +0.71 cm(-1) for the C-bonded form of the dimer.

Infrared spectra of ethylene clusters: (C2D4)2 and (C2D4)3.

Spectra of ethylene dimers and trimers are studied in the ν(11) fundamental band region of C(2)D(4) (≈2200 cm(-1)) using a tuneable quantum cascade laser to probe a pulsed supersonic slit jet expansion. The dimer spectrum is that of a prolate symmetric top perpendicular band, with a distinctive appearance because the A rotational constant is almost exactly equal to six times the B constant. The analysis supports the previously determined cross-shaped dimer structure with D(2d) symmetry. An ethylene trimer has not previously been observed with rotational resolution. The spectrum is that of an oblate symmetric top parallel band. It leads to a proposed trimer structure which is barrel shaped and has C(3h) or C(3) symmetry, with the ethylene monomer C-C axes approximately aligned along the trimer symmetry axis.

Nonpolar nitrous oxide dimer: observation of combination bands of (14N2O)2 and (15N2O)2 involving the torsion and antigeared bending modes.

Spectra of the nonpolar nitrous oxide dimer in the region of the N(2)O ν(1) fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a quantum cascade or a tunable diode laser, with both lasers employed in a rapid-scan signal averaging mode. Four bands were observed and analyzed: new combination bands involving the intermolecular conrotation of the monomers (A(g) antigeared bend) for ((14)N(2)O)(2) and ((15)N(2)O)(2), the previously reported torsional combination band for ((14)N(2)O)(2) with improved signal-to-noise ratio, and the same torsional combination band for ((15)N(2)O)(2). The resulting frequencies for the intermolecular antigeared mode are 96.0926(1) and 95.4912(1) cm(-1) for ((14)N(2)O)(2) and ((15)N(2)O)(2), respectively. This is the third of the four intermolecular frequencies which has now been measured experimentally, the others being the out-of-plane torsion and the geared bend modes. Our experimental results are in good agreement with two recent high level ab initio theoretical calculations.

Soret effect and photochemical reaction in liquids with laser-induced local heating.

We report a theoretical model and experimental results for laser-induced local heating in liquids, and propose a method to detect and quantify the contributions of photochemical and Soret effects in several different situations. The time-dependent thermal and mass diffusion equations in the presence and absence of laser excitation are solved. The two effects can produce similar transients for the laser-on refractive index gradient, but very different laser-off behavior. The Soret effect, also called thermal diffusion, and photochemical reaction contributions in photochemically reacting aqueous Cr(VI)-diphenylcarbazide, Eosin Y, and Eosin Y-doped micellar solutions, are decoupled in this work. The extensive use of lasers in various optical techniques suggests that the results may have significance extending from physical-chemical to biological applications.

Photoacoustic infrared spectroscopy at the Canadian Light Source: commissioning experiments.

The commissioning of synchrotron radiation (SR) photoacoustic (PA) infrared spectroscopy at the Canadian Light Source is described in this article. Aperture tests demonstrated an exponential relationship between the wavenumber where SR and thermal-source PA intensities are equal and beam diameter. Total PA intensity increased linearly with aperture size up to 1.5 mm (SR) or 3 mm (thermal source). At larger apertures, this intensity approached a limiting value. The SR beam diameter in the spectrometer was estimated to be about 0.8 mm in these tests. The low-frequency noise and dc offset that characterize SR PA spectra are suppressed through the calculation of average interferograms prior to Fourier transformation.

Invited article: Linearization and signal recovery in photoacoustic infrared spectroscopy.

Photoacoustic (PA) infrared spectroscopy enables the characterization of a wide variety of materials, affording the spectroscopist several advantages over more traditional infrared methods. While PA spectra are readily acquired using commercial instrumentation, the quality of the data can be improved substantially through the use of specialized numerical and experimental procedures. Two of these methods are the subject of this review. Specifically, this article describes (a) linearization of PA infrared spectra, a calculation that incorporates phase and amplitude information to extend the range of linearity for strongly absorbing samples, and (b) lock-in and digital signal-recovery procedures in step-scan phase-modulation PA infrared spectroscopy. Linearization yields significant improvement in band definition, especially in the low-wavenumber region. This numerical method succeeds in situations where the PA phase of the sample is less than that of the reference (carbon black). When this criterion is not met initially, the sample or reference interferograms can be manipulated prior to the calculation. The steps involved in linearization are illustrated in detail and approximations are discussed. Lock-in demodulation of the step-scan phase-modulation signal is compared to digital (software) demodulation in this study; the lock-in technique is found to be superior in several cases. The imaginary interferograms in these experiments sometimes lack a strong central feature, a situation that necessitates the application of less commonly used methods for phase correction and spectrum calculation. These methods, which are available in commercial software, include two-quadrant and stored-phase corrections. The PA phase spectrum resembles amplitude and absorption spectra when real and imaginary PA spectra are correctly calculated.

Fourier transform Raman spectroscopy of Syncrude Sweet Blend distillation fractions: the 200-1800 cm-1 region.

The fingerprint (200-1800 cm(-1)) region in FT-Raman spectra of Syncrude Sweet Blend (SSB) and its three constituent distillation fractions (naphtha, light gas oil and heavy gas oil) was analyzed in detail in this study. Approximately 50 bands were observed and assigned to functional groups in saturated (alkanes) and unsaturated (aromatics) species. Characteristic bands for mono-, bi-, and tricyclic aromatics were identified and used to quantify these groups in SSB and the distillation fractions. Total aromatics content was determined using the carbon-carbon stretching bands in the 1600-cm(-1) region, and shown to agree with earlier results obtained from the C-H stretching region. The bands due to mono- and bicyclic aromatics permitted calculation of the relative abundances of these species with an accuracy equivalent to that obtained using NMR spectroscopy, a traditional method for measuring this quantity.

Fourier transform Raman spectroscopy of Syncrude sweet blend distillation fractions derived from Athabasca bitumen.

The C-H stretching region in FT-Raman spectra of Syncrude sweet blend (SSB) and three distillation fractions (naphtha, light gas oil and heavy gas oil) was analyzed in detail in this investigation. The frequencies and intensities of the 11 aliphatic and three aromatic C-H bands used to fit the spectrum of SSB were equal to the averages (weighted sums) of the corresponding quantities in the spectra of the fractions. The additivity of the spectra, thought to be a consequence of the large number of discrete compounds contained in each fraction, makes it possible to estimate the composition of other SSB samples using the spectra of the fractions reported in this work. In the aromatic C-H region, total intensities can be used to calculate the distribution of aromatics among the distillation fractions; these data also permit calculation of the fractional aromaticity (per cent aromatic carbon) for SSB and each fraction, with accuracies comparable to those obtained using NMR spectroscopy.

Dual beam photoacoustic infrared spectroscopy of solids using an external cavity quantum cascade laser.

Quantum cascade laser-based instrumentation for dual beam photoacoustic (PA) spectroscopy is described in this article. Experimental equipment includes a 4.55 µm (2141-2265 cm(-1)) continuous wave external cavity quantum cascade laser (EC-QCL), two gas-microphone PA cells, and two lock-in amplifiers. Correction for the time and wavenumber dependence of the laser output is effected through real-time division of the PA signals derived from the sample and reference channels. Source-compensated mid-infrared absorption spectra of carbon black powder and aromatic hydrocarbon solids were obtained to confirm the reliability of the method. Absorption maxima in the EC-QCL PA spectra of hydrocarbons are better defined than those in Fourier transform infrared spectra acquired under similar conditions, enabling the detection of several previously unknown bands.