RESUMEN

We measured the rotationally resolved infrared spectra of helium solvated methyl fluoride at 3 µm and 10 µm, wherein lies C-H and C-F stretching bands, respectively. The linewidths (FWHM) were found to increase with increasing vibrational energy and range from 0.002 cm-1 in the v3 band (C-F stretch) at ~1047 cm-1, to 0.65 cm-1 in the v4 band (asymmetric C-H stretch) at ~2997 cm-1. In between these two bands we observed the lower and upper components of the Fermi triad bands (ν1/2ν2/2ν5) at ~2859 and ~2961 cm-1. We carried out Stark spectroscopy on the lower band on account of its narrower linewidths (0.04 vs. 0.14 cm-1, respectively). The objective of performing Stark spectroscopy was to see if there is any evidence for a rotational linewidth dependence on the external field strength, due to a reduced difference in between methyl fluorides rotational energy gap and the roton-gap of superfluid helium. We did not find any evidence for such an effect, which we largely attribute to the rotational energy gap not increasing significantly enough by the external field. We point to another molecule (formaldehyde) whose energy levels are predicted to show a more promising response to application of an external field.

RESUMEN

Mid-infrared spectra of methanol and methanol-water clusters have been investigated in the symmetric CD3 stretching band of CD3OH and CD3OD. We find that the position of this band provides a useful signature of the general type of hydrogen-bonded cluster it is associated with. Our results are consistent with those previously reported in the OH stretching region (Sulaiman, M. I.; Yang, S.; Ellis, A. M. J. Phys. Chem. A 2017, 121, 771-776) in that methanol clusters from the trimer to the pentamer are cyclic and that mixed clusters with one water molecule (and at least two methanol molecules) are also cyclic. We additionally provide evidence that the methanol trimer adopts a chair-like structure (as opposed to bowl-like), that mixed clusters with a larger number of water molecules are also cyclic, and that branched methanol clusters contribute to the depletion signal in larger methanol clusters. We performed double-hybrid DFT calculations which support these interpretations.

RESUMEN

Rotational emission from vibrationally excited molecules are responsible for a large fraction of lines in the spectra of interstellar molecular clouds. Vinyl alcohol (VA) has two rotamers that differ in energy by 6.4 kJ/mol, both of which have been observed toward the molecular cloud, Sagittarius B2(N) [Turner and Apponi, Astrophys. J. 2001, 561, 207]. Previously, we reported an analysis of the far-infrared spectrum of the higher energy rotamer, anti-VA [Bunn et al. Astrophys. J. 2017, 847, 67], yielding rotational and higher order distortion constants in the first excited vibrational state, and here, we report an analysis of the far-infrared spectrum of the lower energy rotamer, syn-VA, whose spectrum is significantly more complicated on account of Coriolis interactions that result in perturbations to the rovibrational spectrum. We account for those perturbations with the inclusion of Coriolis coupling constants in the fit, which couples the first excited OH torsional (ν15) and CCO bending (ν11) states. Inclusion of them resulted in more physically meaningful rotational and centrifugal distortion constants, and allows for accurate pure rotational line predictions to be made up to high energies. These will be particularly useful in searches for vibrationally excited syn-VA toward warm regions of interstellar molecular clouds, where we predict that it may be significantly abundant.

RESUMEN

Helium is the only solvent within which molecules can "freely" rotate, albeit with an increased moment of inertia relative to the gas phase. Evidence for this can be obtained by performing infrared laser spectroscopy on molecules embedded large helium clusters (nanodroplets), which often reveals rotationally resolved lines that are more closely spaced than in vacuo. The additional rotational inertia results from coupling of the helium to the molecule (rotor), and decreases in going from heavy (e.g., SF6) to light (e.g., CH4) rotors due to a partial breakdown in the adiabatic (following) approximation; faster (lighter) rotors cannot couple as well to helium since their effective interaction with helium is less anisotropic. In addition to this "mass" dependence to the coupling, there is also a time dependence to it, which shows up in the IR spectra as an asymmetry in the rovibrational lineshapes; this results from a delay in the response of helium to the change in rotational speed of the solvated molecule (when ΔJ = ±1). In this perspective we discuss the coupling between various probe molecules and helium that have been investigated by infrared laser spectroscopy in the frequency domain.

RESUMEN

The carbonyl sulfide (OCS) dimer serves as a prototype system for studying intermolecular forces between nonsymmetrical linear polyatomic molecules. Here, we performed a laser spectroscopic investigation of OCS dimers embedded in helium nanodroplets and found rovibrational bands corresponding to the non-polar "sulfur-in" and parallel polar dimers that have been extensively characterized in the gas phase, as well as a new non-polar "oxygen-in" dimer that has long been predicted by theory. Frequency alternations in the rotational branches along with the absence of a Stark effect provided important clues as to its assignment.

RESUMEN

The far-infrared spectrum (100-500 cm-1) of a d1 isotopologue of the astrophysically important molecule, vinyl alcohol, is reported. We observed several low energy (OD) torsional bands: the fundamental and first two hot bands of the syn rotamer and the fundamental and first hot band of the (higher energy) anti rotamer. While the bands corresponding to the anti rotamer are somewhat obscured by rotational lines of water (making a full spectroscopic analysis unfeasible at this stage), the syn-vinyl alcohol bands are not, and a global fit was performed that included 4404 distinct infrared lines assigned in this work, in addition to 59 previously reported microwave lines. This simultaneous analysis of the torsional fundamental, torsional hot band, and pure rotational band of syn-vinyl alcohol allowed for determination of spectroscopic parameters in the first two torsionally excited states and for refinement of them in the ground state. These parameters should be useful in searches for both cold and warm CH2CHOD in interstellar molecular clouds.

RESUMEN

High-resolution, mid-infrared spectra of methanol isotopologues (CH3OH, CH3OD, CD3OH, and CD3OD) embedded in superfluid helium nanodroplets have been obtained. For the normal isotopologue, we observed the CO stretching overtone band, the lines within which are 2× broader than in the fundamental for E species methanol and no different than the fundamental for A species methanol. For CH3OD, we observed the CO stretching overtone band for the first time, which was characterized by narrow line widths for both nuclear spin species. Spectra in the CD3 stretching bands were much broader, which is attributed to rapid relaxation to nearby anharmonically coupled vibrational state(s). Apparently the coupling is much stronger for CD3OD, for which the rotational substructure is completely washed out. Inertial analyses of the rotationally resolved fundamental and overtone bands reveal that the moment of inertia of helium, Δ IHe, that couples to rotation decreases in going from the heavier (CD3OH) to lighter (CH3OH) isotopologues (i.e., with decreasing gas phase moment of inertia, IG). The dependence of Δ IHe on IG is larger than that found for other molecules in regions approaching the heavy and light rotor limits, which suggests a relatively large breakdown in the adiabatic following of helium density for this moderately light rotor.

RESUMEN

The high brightness of the Australian synchrotron allowed for detailed spectra to be collected at high resolution (0.00096 cm-1) in the vicinity of the a/ b/ c-type ν19 band of 2-chloroethanol, which involves O-H torsional motion about the C-O bond. A rovibrational analysis was performed for both chlorine isotopologues in the ν19 fundamental (centered at ∼344 cm-1) which involved the assignment of 7153 lines ( J ≤ 90, K a ≤ 41). A global fit to these lines in addition to 119 microwave lines ( J ≤ 29, K a ≤ 11) led to the determination of spectroscopic constants up to the sextic level in both the ground and excited states using Watson's A-reduction Hamiltonian. The constants agree well with those calculated at the anharmonic MP2/cc-pVTZ level and allow for spectroscopically accurate predictions of rotational transitions in the ground vibrational state to be made over a broad range of rotational energies ( TR < 1000 K). We explored the role that 2-chloroethanol might play in interstellar molecular clouds by performing calculations on the substitution reaction between HCl and ethylene glycol, and the addition reaction between HCl and oxirane, all of which have been observed in Sagittarius B2(N) and are expected to play important roles in the chemistry that occurs on the icy mantles of interstellar dust grains. While both reactions have relatively high activation barriers, the HCl + oxirane reaction was found be much more exothermic; further calculations on it indicate that a water-like environment significantly reduces the barrier while slightly increasing its exothermicity. These results suggest that 2-chloroethanol could be efficiently produced from the cosmic ray bombardment of common interstellar ices.

RESUMEN

We report high-resolution infrared spectra of OCS isotopologues embedded in helium nanodroplets that were recorded with a newly built spectrometer. For the normal isotopologue, we observed the relatively weak third bending overtone band, in addition to new high J transitions in the C-O stretching fundamental, which has previously been investigated by diode laser spectroscopy [S. Grebenev et al., J. Chem. Phys. 112, 4485 (2000)]. Similar to the gas phase, the overtone band is (only) 45 cm-1 higher in energy than the fundamental, and this leads to additional broadening due to rapid vibrational relaxation that is accompanied by the creation of real/virtual phonon excitations. We also observed spectra in the C-O stretching fundamental for several minor isotopologues of OCS, including 18OCS, O13CS, and OC33S, in addition to some new peaks for OC34S. A rovibrational analysis allowed for determination of the moment of inertia of helium (ΔIHe) that couples to the rotation of OCS for each isotopologue. In the context of the adiabatic following approximation, the helium density structure that follows the rotation of OCS should essentially remain unchanged between the isotopologues, i.e., there should be no dependence of ΔIHe on the gas phase moment of inertia of OCS (IG). While this behavior was expected for the "heavy" OCS rotor investigated here, we instead found an approximately linear 1:1 relation between ΔIHe and IG, which suggests partial breakdown of the adiabatic following approximation, making OCS the heaviest molecule for which evidence for this effect has been obtained.

RESUMEN

The entrance channel complex in the exothermic OH + CH4 → H2O + CH3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (jCH4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same for all internal rotation states; however, subband origins are found to decrease with increasing jCH4. Measurements of deuterated complexes have also been made (OD-CH4, OH-CD4, and OD-CD4), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH-CH4 and OD-CD4, for which the excited OX stretching state has a nearby CY4 stretching fundamental (X, Y = H or D).

RESUMEN

We report the Fourier transform microwave spectra of (pH2)N-13C16O, (pH2)N-12C18O, and (pH2)N-13C18O (N ≤ 8) clusters. We find that the frequencies of the a-type J = 1-0 transitions decrease to a minimum at N = 6 and then rapidly increase up to at least N = 8; this is similar to what was previously reported for (pH2)N-12C16O, for which the turnaround was found to correlate with an increase in the superfluid fraction of the pH2 component of the clusters [ Raston Phys. Rev. Lett. 2012 , 108 , 253402 ]. The data suggest that the turnaround in the transition frequency marks an abrupt decrease in the anisotropy of the potential (i.e., in going from N = 6 → 7 → 8), as evidenced from the isotopologic differences rapidly evolving from end-over-end to free-rotor character. Structurally, a more quantitative analysis of the anisotropy was hindered by the lack of accurate frequencies in the b-type series, and a simple Kraitchman analysis yielded unphysical results. In addition to comparing the transition frequencies of the different isotopologic clusters, we provide here more comprehensive details and further discussion of the initial measurements made on (pH2)N-12C16O.

RESUMEN

Sequential capture of OH and CO by superfluid helium droplets leads exclusively to the formation of the linear, entrance-channel complex, OH-CO. This species is characterized by infrared laser Stark and Zeeman spectroscopy via measurements of the fundamental OH stretching vibration. Experimental dipole moments are in disagreement with ab initio calculations at the equilibrium geometry, indicating large-amplitude motion on the ground state potential energy surface. Vibrational averaging along the hydroxyl bending coordinate recovers 80% of the observed deviation from the equilibrium dipole moment. Inhomogeneous line broadening in the zero-field spectrum is modeled with an effective Hamiltonian approach that aims to account for the anisotropic molecule-helium interaction potential that arises as the OH-CO complex is displaced from the center of the droplet.

RESUMEN

Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH-H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH-H2O and OH-D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for "up-up" and "up-down" structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm(-1) to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.

RESUMEN

The T-shaped OH-C2H2 complex is formed in helium droplets via the sequential pick-up and solvation of the monomer fragments. Rovibrational spectra of the a-type OH stretch and b-type antisymmetric CH stretch vibrations contain resolved parity splitting that reveals the extent to which electronic angular momentum of the OH moiety is quenched upon complex formation. The energy difference between the spin-orbit coupled (2)B1 (A″) and (2)B2 (A') electronic states is determined spectroscopically to be 216 cm(-1) in helium droplets, which is 13 cm(-1) larger than in the gas phase [Marshall et al., J. Chem. Phys. 121, 5845 (2004)]. The effect of the helium is rationalized as a difference in the solvation free energies of the two electronic states. This interpretation is motivated by the separation between the Q(3/2) and R(3/2) transitions in the infrared spectrum of the helium-solvated (2)Π3/2 OH radical. Despite the expectation of a reduced rotational constant, the observed Q(3/2) to R(3/2) splitting is larger than in the gas phase by ≈0.3 cm(-1). This observation can be accounted for quantitatively by assuming the energetic separation between (2)Π3/2 and (2)Π1/2 manifolds is increased by ≈40 cm(-1) upon helium solvation.

RESUMEN

We report the Fourier transform microwave spectra of the a-type J = 1-0 transitions of the binary and ternary CO-(pH2)2, CO-pH2-He, CO-HD, and CO-(oD2)N=1,2 clusters. In addition to the normal isotopologue of CO for all clusters, we observed the transitions of the minor isotopologues, (13)C(16)O, (12)C(18)O, and (13)C(18)O, for CO-(pH2)2 and CO-pH2-He. All transitions lie within 335 MHz of the experimentally or theoretically predicted values. In comparison to previously reported infrared spectra [Moroni et al., J. Chem. Phys. 122, 094314 (2005)], we are able to tentatively determine the vibrational shift for CO-pH2-He, in addition to its b-type J = 1-0 transition frequency. The a-type frequency of CO-pH2-He is similar to that of CO-He2 [Surin et al., Phys. Rev. Lett. 101, 233401 (2008)], suggesting that the pH2 molecule has a strong localizing effect on the He density. Perturbation theory analysis of CO-oD2 reveals that it is approximately T-shaped, with an anisotropy of the intermolecular potential amounting to ∼9 cm(-1).

RESUMEN

Vibrational spectroscopy and helium nanodroplet isolation are used to determine the gas-phase thermochemistry for isomerization between conformations of the model dipeptide, N-acetylglycine methylamide (NAGMA). A two-stage oven source is implemented to produce a gas-phase equilibrium distribution of NAGMA conformers, which is preserved when individual molecules are captured and cooled to 0.4 K by He nanodroplets. With polarization spectroscopy, the IR spectrum in the NH stretch region is assigned to a mixture of two conformers having intramolecular hydrogen bonds composed of either five- or seven-membered rings, C5 and C7, respectively. The C5 to C7 interconversion enthalpy and entropy, obtained from a van't Hoff analysis, are -4.52 ± 0.12 kJ/mol and -12.4 ± 0.2 J/(mol · K), respectively. The experimental thermochemistry is compared to high-level electronic structure theory computations.

Asunto(s)

RESUMEN

Methanol is one of the simplest molecules that undergo torsional oscillations, and so it has been extensively studied in the gas phase by various spectroscopic techniques. At 300 K, a large number of rotational, torsional, and vibrational energy levels is populated, and this makes for a rather complicated spectrum, which is still not fully understood. It is expected that in going from 300 K to 0.4 K (the temperature of helium nanodroplets) the population distribution of methanol will mainly collapse into two states; the JK = 00 state for the A1 nuclear spin symmetry species (with ICH3 = 3/2), and the JK = 1-1 state for the E species (ICH3 = 1/2). This results in a simplified spectrum that consists of narrow a-type (ΔK = 0) lines and broader b- and c-type (ΔK = ±1) lines. We have recorded the rotovibrational spectrum of CH3OH in the OH stretching, CH3 stretching and bending, CH3 rocking, and CO stretching regions, and have firmly assigned five bands (v1, v2, v3, v7, and v8), and tentatively assigned five others (v9, 2v4, v4 + v10, 2v10, and v4 + v5). To our knowledge, the transitions we have assigned within the v4 + v10, 2v10, and v4 + v5 bands have not yet been assigned in the gas phase, and we hope that considering the very small "matrix" shift in helium nanodroplets (<1 cm(-1) for most subband origins of CH3OH), those made here can aid in their gas phase identification. Microwave-infrared double resonance spectroscopy was used to confirm the initially tentative a-type infrared assignments in the OH stretching (v1) band of A1 species methanol, in addition to revealing "warm" b-type lines. From a rotovibrational analysis, the B rotational constant is found to be reduced quite significantly (56%) with respect to the gas phase, and the torsional tunneling splittings are relatively unaffected and are at most reduced by 16%. While most rovibrational peaks are Lorentzian shaped, and those which are significantly perturbed by vibrational coupling in the gas phase are additionally broadened, the narrowest ΔJ = +1 peaks are asymmetric, and a skew-type analysis suggests that the response time of the helium solvent upon excitation is of the order of 1 ns.

RESUMEN

This work extends our earlier investigation of the near-infrared absorption spectroscopy of atomic bromine (Br) trapped in solid parahydrogen (pH2) and orthodeuterium (oD2) [S. C. Kettwich, L. O. Paulson, P. L. Raston, and D. T. Anderson, J. Phys. Chem. A 112, 11153 (2008)]. We report new spectroscopic observations on a series of double transitions involving excitation of the weak Br-atom spin-orbit (SO) transition ((2)P(1/2) ← (2)P(3/2)) in concert with phonon, rotational, vibrational, and rovibrational excitation of the solid molecular hydrogen host. Further, we utilize the rapid vapor deposition technique to produce pH2 crystals with a non-equilibrium mixture of face centered cubic (fcc) and hexagonal closed packed (hcp) crystal domains in the freshly deposited solid. Gentle annealing (T = 4.3 K) of the pH2 sample irreversibly converts the higher energy fcc crystal domains to the slightly more stable hcp structure. We follow the extent of this conversion process using the intensity of the U1(0) transition of solid pH2 and correlate crystal structure changes with changes in the integrated intensity of Br-atom absorption features. Annealing the pH2 solid causes the integrated intensity of the zero-phonon Br SO transition to increase approximately 45% to a value that is 8 times larger than the gas phase value. We show that the magnitude of the increase is strongly correlated to the fraction of hcp crystal domains within the solid. Theoretical calculations presented in Paper II show that these intensity differences are caused by the different symmetries of single substitution sites for these two crystal structures. For fully annealed Br-atom doped pH2 solids, where the crystal structure is nearly pure hcp, the Br-atom SO transition sharpens considerably and shows evidence for resolved hyperfine structure.

RESUMEN

The ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was vaporized at 420 K, and the ion-pair constituents were entrained in a beam of liquid He nanodroplets and cooled to 0.4 K. The vapor pressure was optimized such that each He droplet picked up a single ion-pair from the gas phase. Infrared spectroscopy in the CH stretch region reveals bands that are assigned to intact ion-pairs on the basis of comparisons to ab initio harmonic frequency computations of 23 low energy isomers. The He droplet spectrum is consistent with a weighted sum of the computed harmonic spectra, in which the weights are determined from ab initio computations of the relative free energies at 420 K. Anharmonic resonance polyads in the CH stretch region are treated explicitly, which improves the agreement between the experiment and computed spectra for ion-pairs. For isomers having a strong cation···anion hydrogen bonding interaction, the imidazolium C(2)-H stretch fundamental is shifted to lower energy and into resonance with the overtones and combination bands of the imidazolium ring stretching modes, resulting in a spectral complexity in the CH stretch region that is fully resolved in the He droplet spectrum. The assignment of the infrared spectrum to ion-pairs is confirmed through polarization spectroscopy measurements that reveal the permanent electric dipole moment of the He-solvated species to be 11 ± 2 D. The computed permanent electric dipole moments for the low energy isomers of the [emim(+)][Tf2N(-)] ion-pairs fall in the range 9-13 D, whereas the computed dipole moments of decomposition products of the ionic liquid are less than 4.3 D.