The HOOO radical has long been postulated to be an important intermediate in atmospherically relevant reactions and was recently deemed a significant sink for OH radicals in the tropopause region. In the present experiments, HOOO radicals are generated in a pulsed supersonic expansion by the association of O(2) and photolytically generated OH radicals, and the spectral signature and vibrational predissociation dynamics are investigated via IR action spectroscopy, an IR-UV double resonance technique. Rotationally resolved IR action spectra are obtained for trans-HOOO in the fundamental (nu(OH)) and overtone (2nu(OH)) OH stretching regions at 3569.30 and 6974.18 cm(-1), respectively. The IR spectra exhibit homogeneous line broadening, characteristic of a approximately 26-ps lifetime, which is attributed to intramolecular vibrational redistribution and/or predissociation to OH and O2 products. In addition, an unstructured feature is observed in both the OH fundamental and overtone regions of HOOO, which is likely due to cis-HOOO. The nascent OH X(2)Pi, v = 0 or v = 1, products following vibrational predissociation of HOOO, nu(OH) or 2nu(OH), respectively, have been investigated using saturated laser-induced fluorescence measurements. A distinct preference for population of Pi(A') Lambda-doublets in OH was observed and is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained.

Hydrogen trioxy (HOOO) and its deuterated analog (DOOO) have been generated in a supersonic free-jet expansion through association of photolytically generated OH or OD and molecular oxygen. The radicals were detected using infrared action spectroscopy, a highly sensitive double resonance technique. Rotationally resolved spectra of combination bands of HOOO and DOOO comprising one quantum of OH or OD stretch (nu(1)) and one quantum of a lower frequency mode (nu(1)+nu(n) where n=3-6), including HDOO bend (nu(3)), OOO bend (nu(4)), central OO stretch (nu(5)), and HDOOO torsion (nu(6)), have been observed and assigned to the trans conformer. All but one of these bands are accompanied by unstructured features which are tentatively assigned to the corresponding vibration of the cis conformer. In total, five additional bands of HOOO and four of DOOO have been recorded and assigned. These data represent the first gas-phase observation of the low-frequency modes of HOOO and DOOO and they are found to differ significantly from previous matrix studies and theoretical predictions. Accurate knowledge of the vibrational frequencies is crucial in assessing thermochemical properties of HOOO and present possible means of detection in the atmosphere.

The hydrogen trioxy radical (HO3) has been proposed as an intermediate in several important chemical reactions and relaxation processes involving OH in the atmosphere. In this work, the gas-phase infrared action spectrum of HO3 is obtained in the OH overtone region, along with the product state distribution of the OH fragment following dissociation. The highest observed OH product channel sets an upper limit for the HO-O2 binding energy of 6.12 kcal mol(-1). The experimental stability of HO3 and derived equilibrium constant imply that up to 66% of atmospheric OH may be converted into HO3 in the tropopause region.

Weakly bound molecules--particularly hydrated complexes of abundant atmospheric species--have long been postulated to play an important role in atmospherically relevant reactions. For example, such complexes could seed cloud formation and alter the global radiation budget. In this Account, we initially describe the current data on weakly bound species produced in association reactions of the hydroxyl radical (OH) with molecular partners, particularly oxygen (O(2)), nitric acid (HONO(2)), and nitrogen dioxide (NO(2)). Researchers have identified weakly bound association products of these reactions as the hydrogen trioxy (HOOO) radical, the doubly hydrogen-bonded OH-HONO(2) complex, and peroxynitrous acid (HOONO), respectively. In each case, previous kinetic studies of the reaction or OH vibrational relaxation processes have indicated unusual, non-Arrhenius behavior. Under the temperature-pressure conditions of the Earth's lower atmosphere, these processes exhibit a negative temperature dependence, indicative of an attractive interaction, or a pressure dependence. Researchers have subsequently carried out extensive theoretical studies of the properties of these weakly bound molecules, but the theoretical studies have lacked experimental validation. Next, we describe experimental studies to determine the vibrational frequencies and stability of HOOO as a prototypical example of these weakly bound molecules. We then use these data to assess its importance in the atmosphere. We discuss the efficient production of the HOOO radical from OH and O(2) under laboratory conditions and its subsequent detection using infrared action spectroscopy, a highly sensitive and selective double resonance technique. Using excitation of OH stretch and combination bands comprising OH stretch with lower frequency modes, we obtain detailed spectroscopic information on the vibrational modes of the two conformers of HOOO. In addition, we infer fundamental information about the dissociation dynamics from the OH product state distribution, which provides insight into the chemical bonding in HOOO. Perhaps most importantly, we utilize a simple conservation of energy relationship based on the highest energetically open OH product state to derive a rigorous upper limit for the stability of HOOO relative to the OH + O(2) asymptote of 5.3 kcal mol(-1). When combined with previous experimental rotational constants that reflect the structure of the HOOO radical, our laboratory characterization of its stability and vibrational frequencies provides critical information to assess its thermochemical properties. Using standard statistical mechanics approaches, we can calculate the likely atmospheric abundance of HOOO. We estimate that up to 25% of the OH radicals in the vicinity of the tropopause may be associated with O(2) as a weakly bound molecule.

The DOOO radical has been produced by three-body association between OD and O2 in a supersonic free-jet expansion and investigated using action spectroscopy, an IR-UV double-resonance technique. Partially rotationally structured bands observed at 2635.06 and 5182.42 cm(-1) are assigned to the OD stretch fundamental (nu(OD)) and overtone (2nu(OD)), respectively, of the trans-DOOO radical. Unstructured bands observed in both spectral regions are assigned to cis-DOOO. Nascent OD X(2)Pi product state distributions following vibrational predissociation appear to be nearly statistical with respect to the degree of rotational excitation, but display a marked propensity for Pi(A') Lambda-doublets, which is interpreted as a signature of a planar dissociation. The energetically highest open OD X(2)Pi product channel implies an upper limit dissociation energy D0 < or = 1856 cm(-1) or 5.31 kcal mol(-1). This value allows refinement of the upper limit D0 of the atmospherically important HOOO isotopomer, suggesting that it is marginally less stable than previously thought.