Laser spectroscopic studies of the pure rotational U_0(0) and W_0(0) transitions of solid parahydrogen

High resolution spectrum of multipole-induced transitions of solid parahydrogen was recorded using diode and difference frequency laser spectroscopy. The J=4<--0 pure rotational U_0(0) transition observed in the diode spectrum agrees well in frequency with the value reported by Balasubramanian et al. [Phys. Rev. Lett. 47, 1277 (1981)] but we observed a spectral width smaller by about a factor of 4. The J=6<--0 W_0(0) transition was observed to be exceedingly sharp, with a width of ~70 MHz, using a difference frequency spectrometer with tone-burst modulation. This transition is composed of three components with varying relative intensity depending upon the direction of polarization of laser radiation. These components were interpreted as the splitting of the M levels in the J=6 state due to crystal field interactions. In addition, a new broad feature was found at 2452.4 cm^(−1) in the low resolution Fourier-transform infrared (FTIR) spectrum of solid hydrogen and was assigned to be the phonon branch W_R(0) transition of the W_0(0) line. The selection rules, crystal field splitting of J=4 and J=6 rotons, and the measured linewidth based on these observations are discussed

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO (peroxynitrous acid). The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple zeta basis set, at the structure optimized using the triple zeta basis set (CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ). The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD(T)/cc-pVTZ and QCISD/AUG-cc-pVTZ (QCISD—quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions) level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at ~90°, the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2nuOH region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+NO2 and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D0=82.0 kJ/mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to Delta n=0 transitions (where n is the HOON torsion quantum number) that are blue shifted relative to the origin band, while the large peak near 7000 cm^–1 is assigned to a series of Delta n=+1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO (6300–6850 cm^–1) is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm^–1 and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations

lntracluster rearrangement of protonated nitric acid: Infrared spectroscopic studies of H^+(HNO_3)(H_2O)_n

Infrared spectra of clusters of protonated nitric acid and water exhibit a marked change with cluster size, indicating that an intracluster reaction occurs with sufficient solvation. In small clusters, H_2O binds to a nitronium ion core, but at a critical cluster size the NO^+_2 reacts. A lower bound of 174 kcal/mol is found for the proton affinity of HNO_3

Vibrational spectroscopy of NO^+(H_2O)_n: Evidence for the intracluster reaction NO^+(H_2O)_n→H_3O^+(H_2O)_(n-2)(HONO) at n≥4

Infrared spectra of mass‐selected clusters NO^+(H_2O)_n for n=1 to 5 were recorded from 2700 to 3800 cm^(−1) by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second‐order Møller–Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H_2O ligands bound to a nitrosonium ion NO^+ core. They possessed perturbed H_2O stretch bands and dissociated by loss of H_2O. The H_2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm^(−1) and two new minor photodissociation channels, loss of HONO and loss of two H_2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H_3O^+(H_2O)_3(HONO), i.e., an adduct of the reaction products

Generation of energetic He atom beams by a pulsed positive corona discharge

Time-of-flight measurements were made of neutral helium atom beams extracted from a repetitive, pulsed, positive-point corona discharge. Two strong neutral peaks, one fast and one slow, were observed, accompanied by a prompt photon peak and a fast ion peak. All peaks were correlated with the pulsing of the discharge. The two types of atoms appear to be formed by different mechanisms at different stages of the corona discharge. The fast atoms had energies of 190 eV and were formed at the onset of the pulsing, approximately 0.7 µs before the maximum of the photon peak. The slow peak, composed of electronically metastable He atoms, originated 30–50 µs after the photon pulse, and possessed a nearly thermal velocity distribution. The velocity distribution was typical of an undisturbed supersonic expansion with a stagnation temperature of 131 K and a speed ratio of 3.6. Peak intensities and velocities were measured as a function of source voltage, stagnation pressure, and skimmer voltage

Cis-cis and trans-perp HOONO: Action spectroscopy and isomerization kinetics

The weakly bound HOONO product of the OH + NO_2 + M reaction is studied using the vibrational predissociation that follows excitation of the first OH overtone (2nu1). We observe formation of both cis-cis and trans-perp conformers of HOONO. The trans-perp HOONO 2nu1 band is observed under thermal (223–238 K) conditions at 6971 cm^(–1). We assign the previously published (warmer temperature) HOONO spectrum to the 2nu1 band at 6365 cm^(–1) and 2nu1-containing combination bands of the cis-cis conformer of HOONO. The band shape of the trans-perp HOONO spectrum is in excellent agreement with the predicted rotational contour based on previous experimental and theoretical results, but the apparent origin of the cis-cis HOONO spectrum at 6365 cm^(–1) is featureless and significantly broader, suggesting more rapid intramolecular vibrational redistribution or predissociation in the latter isomer. The thermally less stable trans-perp HOONO isomerizes rapidly to cis-cis HOONO with an experimentally determined lifetime of 39 ms at 233 K at 13 hPa (in a buffer gas of predominantly Ar). The temperature dependence of the trans-perp HOONO lifetime in the range 223–238 K yields an isomerization barrier of 33±12 kJ/mol. New ab initio calculations of the structure and vibrational mode frequencies of the transition state perp-perp HOONO are performed using the coupled cluster singles and doubles with perturbative triples [CCSD(T)] model, using a correlation consistent polarized triple zeta basis set (cc-pVTZ). The energetics of cis-cis, trans-perp, and perp-perp HOONO are also calculated at this level [CCSD(T)/cc-pVTZ] and with a quadruple zeta basis set using the structure determined at the triple zeta basis set [CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ]. These calculations predict that the anti form of perp-perp HOONO has an energy of DeltaE0 = 42.4 kJ/mol above trans-perp HOONO, corresponding to an activation enthalpy of DeltaH298[double-dagger]0 = 41.1 kJ/mol. These results are in good agreement with statistical simulations based on a model developed by Golden, Barker, and Lohr. The simulated isomerization rates match the observed decay rates when modeled with a trans-perp to cis-cis HOONO isomerization barrier of 40.8 kJ/mol and a strong collision model. The quantum yield of cis-cis HOONO dissociation to OH and NO2 is also calculated as a function of photon excitation energy in the range 3500–7500 cm^(–1), assuming D0 = 83 kJ/mol. The quantum yield is predicted to vary from 0.15 to 1 over the observed spectrum at 298 K, leading to band intensities in the action spectrum that are highly temperature dependent; however, the observed relative band strengths in the cis-cis HOONO spectrum do not change substantially with temperature over the range 193–273 K. Semiempirical calculations of the oscillator strengths for 2nu1(cis-cis HOONO) and 2nu1(trans-perp HOONO) are performed using (1) a one-dimensional anharmonic model and (2) a Morse oscillator model for the OH stretch, and ab initio dipole moment functions calculated using Becke, Lee, Yang, and Parr density functional theory (B3LYP), Møller-Plesset pertubation theory truncated at the second and third order (MP2 and MP3), and quadratic configuration interaction theory using single and double excitations (QCISD). The QCISD level calculated ratio of 2nu1 oscillator strengths of trans-perp to cis-cis HOONO is 3.7:1. The observed intensities indicate that the concentration of trans-perp HOONO early in the OH + NO2 reaction is significantly greater than predicted by a Boltzmann distribution, consistent with statistical predictions of high initial yields of trans-perp HOONO from the OH + NO_2 + M reaction. In the atmosphere, trans-perp HOONO will isomerize nearly instantaneously to cis-cis HOONO. Loss of HOONO via photodissociation in the near-IR limits the lifetime of cis-cis HOONO during daylight to less than 45 h, other loss mechanisms will reduce the lifetime further

Infrared spectrum of the silicon hydride cation SiH_7^+

Silanium ions are an important class of hypervalent molecules, and the determination of their structure will yield insights into the nature of nonclassical bonding and provide a contrast to the bonding in carbonium ions. We report the infrared spectrum of the mass-selected silicon hydride cluster ion ^(28)SiH_7^+ detected by vibrational predissociation spectroscopy. Silanium ions were formed in a pulsed high pressure glow discharge and cooled by the subsequent supersonic expansion. Photodissociation spectra were obtained using a tandem time-of-flight mass spectrometer: (formula available in paper) ions were mass-selected and excited by a tunable infrared laser. The resulting photofragments were detected using a reflectron as a mass analyzer. We observed a vibrational band at 3865 cm^(-1), which was the only one observed from 3500 cm^(-1) to 4200 cm^(-1). This result suggests that the molecule might form a symmetric complex with the structure H_2⋅SiH_3^+⋅H_2, in contrast to the CH_7^+ which has the structure CH_5^+⋅H_2

Infrared spectrum of the silicon hydride cation SiH_7^+

Silanium ions are an important class of hypervalent molecules, and the determination of their structure will yield insights into the nature of nonclassical bonding and provide a contrast to the bonding in carbonium ions. We report the infrared spectrum of the mass-selected silicon hydride cluster ion ^(28)SiH_7^+ detected by vibrational predissociation spectroscopy. Silanium ions were formed in a pulsed high pressure glow discharge and cooled by the subsequent supersonic expansion. Photodissociation spectra were obtained using a tandem time-of-flight mass spectrometer: (formula available in paper) ions were mass-selected and excited by a tunable infrared laser. The resulting photofragments were detected using a reflectron as a mass analyzer. We observed a vibrational band at 3865 cm^(-1), which was the only one observed from 3500 cm^(-1) to 4200 cm^(-1). This result suggests that the molecule might form a symmetric complex with the structure H_2⋅SiH_3^+⋅H_2, in contrast to the CH_7^+ which has the structure CH_5^+⋅H_2

Infrared Spectra of Mass-Selected Br¯−(NH_3)_n and I¯−NH_3 Clusters

Infrared vibrational predissociation spectra are recorded for Br¯−(NH_3)_n (n = 1−4) and I¯−NH_3 clusters in the N−H stretch region (3040−3460 cm^(−1)). To aid spectral assignments and clarify structures of the Br¯−(NH_3)_n clusters, ab initio calculations are performed at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVTZ levels of theory. The Br¯−NH_3 and I¯−NH_3 dimers are predicted to have structures in which the NH_3 molecule is attached to the halide anion by a single hydrogen-bond. The dominant infrared band for Br¯−NH_3 at 3171 cm^(−1) corresponds to a hydrogen-bonded N−H stretch vibrational mode, whereas two weaker bands are assigned to a symmetric stretch vibration of the nonbonded N−H groups (3347 cm^(−1)) and to an ammonia-based bending overtone (3293 cm^(−1)) deriving infrared intensity through Fermi interaction with the H-bonded N−H stretch mode. The corresponding I¯−NH3 spectrum is dominated by the H-bonded N−H stretch band at 3217 cm^(−1), with three weaker bands at 3240, 3305, and 3360 cm^(−1) assigned to two bending overtone vibrations and the nonbonded N−H symmetric stretch vibration, respectively. Spectra of the Br¯−(NH_3)_n, n = 2−4, clusters are similar to the I¯−NH_3 spectrum, exhibiting evidence for strong Fermi interactions between the H-bonded N−H stretch vibrational mode and ammonia-based bending overtones. On the basis of the infrared spectra and ab initio calculations, the larger Br¯−(NH_3)_n clusters are deduced to have structures in which the NH_3 molecules are attached to the Br¯ by single H-bonds, but not necessarily to one other