Mitchio Okumura

Infrared spectra of the cluster ions H7O+3⋅H2 and H9O+4⋅H2

Infrared spectra of hydrated hydronium ions weakly bound to an H2 molecule, specifically H7O + 3 ·H2 and H9O + 4 ·H2, have been observed. Mass-selected parent ions, trapped in a radio frequency ion trap, are excited by a tunable infrared laser; following absorption, the complex predissociates with loss of the H2, and the resulting fragment ions are detected. Spectra have been taken from 3000 to 4000 cm^−1, with a resolution of 1.2 cm^−1. They are compared to recent theoretical and experimental spectra of the hydronium ion hydrates alone. Binding an H2 molecule to these clusters should only weakly perturb their vibrations; if so, our spectra should be similar to spectra of the hydrated hydronium ions H7O + 3 and H9O + 4 .

The vibrational predissociation spectroscopy of hydrogen cluster ions

Although molecular ion spectroscopy has progressed rapidly[1], there has been very little spectroscopy done of weakly bound ionic clusters[2,3]. These clusters play an important role in atmospheric chemistry and have been studied extensively in thereto-chemical and kinetic experiments over the past decade[4]. Much of our understanding of the dynamics and structure of cluster ions to date has relied on the results of ab initio quantum calculations. Stimulated by the theoretical work, we have begun experiments on the infrared spectroscopy of cluster ions, and have recently made the first spectroscopic observation of the protonated hydrogen clusters H n + (n=5,7,9,11,13 and 15).

Infrared spectroscopy of the cluster ions H+3⋅(H2)n

The vibrational spectra of the clusters H + 3 (H2)n were observed near 4000 cm−1 by vibrational predissociation spectroscopy. Spectra of mass-selected clusters were obtained by trapping the ions in a radio frequency ion trap, exciting vibrational transitions of the cluster ions to predissociating levels, and detecting the fragment ions with a mass spectrometer. Low resolution bands of the solvent H2 stretches were observed for the clusters of one to six H2 coordinated to an H + 3 ion. The red shift of these vibrations relative to the monomer H2 frequency supported the model of H + 9 as an H + 3 with a complete inner solvation shell of three H2, one bound to each corner of the ion. Two additional bands of H + 5 were observed, one assigned as the H + 3 symmetric stretch, and the other as a combination or overtone band. High-resolution scans (0.5 and 0.08 cm−1) of H + n , n=5, 7, and 9 yielded no observable rotational structure, a result of either spectral congestion or rapid cluster dissociation. The band contour of the H + 5 band changed upon cooling the internal degrees of freedom, but the peaks remained featureless. The observed frequencies of H + 7 and H + 9 agreed well with ab initio predictions, but those of H + 5 did not. This deviation is discussed in terms of the large expected anharmonicity of the proton bound dimer H + 5 .

Rate of Gas Phase Association of Hydroxyl Radical and Nitrogen Dioxide

Honing in on HONO2 Modeling air pollution requires knowledge of all the interrelated reactions occurring in the atmosphere. Among the most significant is the formation of nitric acid (HONO2) from OH and NO2 radicals. One sticking point in the study of this reaction has been the uncertainty in how often radicals link through an O-O rather than an O-N bond. Mollner et al. (p. 646) measured the partitioning coefficient, as well as the overall consumption rate of the radicals, with an array of highly sensitive spectroscopic techniques in the laboratory. The measurements yielded a well-defined rate constant for nitric acid formation, which was applied to the prediction of ozone levels in atmospheric simulations of the Los Angeles basin. Laboratory measurements of a critical atmospheric rate constant should improve predictions of tropospheric ozone formation. The reaction of OH and NO2 to form gaseous nitric acid (HONO2) is among the most influential in atmospheric chemistry. Despite its importance, the rate coefficient remains poorly determined under tropospheric conditions because of difficulties in making laboratory rate measurements in air at 760 torr and uncertainties about a secondary channel producing peroxynitrous acid (HOONO). We combined two sensitive laser spectroscopy techniques to measure the overall rate of both channels and the partitioning between them at 25°C and 760 torr. The result is a significantly more precise value of the rate constant for the HONO2 formation channel, 9.2 (±0.4) × 10−12 cm3 molecule−1 s−1 (1 SD) at 760 torr of air, which lies toward the lower end of the previously established range. We demonstrate the impact of the revised value on photochemical model predictions of ozone concentrations in the Los Angeles airshed.

Vibrational spectrum of I−(H2O)

Abstract The infrared spectrum of the ionic cluster I−(H2O) was recorded from 3170 to 3800 cm−1 by vibrational predissociation spectroscopy. A strong multiplet observed at 3415 cm−1 and a narrow band at 3710 cm−1 were assigned as a hydrogen-bonded OH stretch and free OH stretch respectively, indicating that H2O forms a single hydrogen bond with the iodide anion. Ab initio vibrational frequencies and intensities were computed at the second-order Moller-Plesset (MP2) level for the minimum energy configuration, a nearly linear hydrogen-bonded isomer, and for a low-lying saddlepoint, a symmetric C2v bridged isomer. The spectrum predicted for the hydrogen-bonded isomer agreed well with experiment.

The air-broadened, near-infrared CO2 line shape in the spectrally isolated regime: Evidence of simultaneous Dicke narrowing and speed dependence

Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was employed to measure air-broadened CO(2) line shape parameters for transitions near 1.6 μm over a pressure range of 6.7-33 kPa. The high sensitivity of FS-CRDS allowed for the first measurements in this wavelength range of air-broadened line shape parameters on samples with CO(2) mixing ratios near those of the atmosphere. The measured air-broadening parameters show several percent deviations (0.9%-2.7%) from values found in the HITRAN 2008 database. Spectra were fit with a variety of models including the Voigt, Galatry, Nelkin-Ghatak, and speed-dependent Nelkin-Ghatak line profiles. Clear evidence of line narrowing was observed, which if unaccounted for can lead to several percent biases. Furthermore, it was observed that only the speed-dependent Nelkin-Ghatak line profile was able to model the spectra to within the instrumental noise level because of the concurrent effects of collisional narrowing and speed dependence of collisional broadening and shifting.

Vibrational spectroscopy of NO+(H2O)n: Evidence for the intracluster reaction NO+(H2O)n→H3O+(H2O)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 Moller–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.

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals

We demonstrate time-resolved frequency comb spectroscopy (TRFCS), a new broadband absorption spectroscopy technique for the study of trace free radicals on the microsecond timescale. We apply TRFCS to study the time-resolved, mid-infrared absorption of the deuterated hydroxyformyl radical trans-DOCO, an important short-lived intermediate along the OD + CO reaction path. Directly after photolysis of the chemical precursor acrylic acid-d1, we measure absolute trans-DOCO product concentrations with a sensitivity of 5 × 10(10) cm(-3) and observe its subsequent loss with a time resolution of 25 μs. The multiplexed nature of TRFCS allows us to detect simultaneously the time-dependent concentration of several other photoproducts and thus unravel primary and secondary chemical reaction pathways.

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

The weakly bound HOONO product of the OH+NO2+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+NO2+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.

Primary and secondary dissociation pathways in the ultraviolet photolysis of Cl2O

The photodissociation of dichlorine monoxide (Cl_2O) at 308, 248, and 193 nm was studied by photofragment translational energy spectroscopy. The primary channel upon excitation at 308 and 248 nm was Cl–O bond fission with production of ClO+Cl. A fraction of the ClO photoproducts also underwent spontaneous secondary dissociation at 248 nm. The center-of-mass translational energy distribution for the ClO+Cl channel at 248 nm appeared to be bimodal with a high energy component that was similar in shape to the 308 nm distribution and a second, low energy component with a maximum close to the threshold for the 2Cl+O(3P) channel. Observation of a bimodal distribution suggests that two pathways with different dissociation dynamics lead to ClO+Cl products. The high product internal energy of the second component raises the possibility that ClO is formed in a previously unobserved spin-excited state a 4∑−. Following excitation at 193 nm, a concerted dissociation pathway leading to Cl_2+O was observed in addition to primary Cl–O bond breakage. In both processes, most of the diatomic photofragments were formed with sufficient internal energy that they spontaneously dissociated. The time-of-flight distributions of the Cl_2+O products suggest that these fragments are formed in two different channels Cl_2(3II)+O(3P) and Cl_2(X1∑)+O(1D).