Timothy D. Sechler

Weakly Bound Molecules in the Atmosphere: A Case Study of HOOO

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 Earths 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.

Observation of ν1+νn combination bands of the HOOO and DOOO radicals using infrared action spectroscopy

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.

Vibrational energy in molecules probed with high time and space resolution

This article reviews experimental measurements of vibrational energy in condensed-phase molecules that simultaneously provide time resolution of picoseconds and spatial resolution of ångströms. In these measurements, ultrashort light pulses are used to input vibrational energy and probe dynamical processes. High spatial resolution is obtained using vibrational reporter groups in known locations on the molecules. Three examples are discussed in detail: (1) vibrational energy flow across molecules in a liquid from an OH–group to a CH3–group; (2) vibrational energy flow across a molecular surfactant monolayer that separates an aqueous and a non-polar phase in a suspension of reverse micelles; and (3) vibrational energy input by laser-driven shock waves to a self-assembled monolayer of long-chain alkane molecules. These experiments provide new insights into the movement of mechanical energy over short length and time scales where ordinary concepts of heat conduction no longer apply, where the concepts of quantum mechanical energy transfer reign supreme.

Measuring properties of interfacial and bulk water regions in a reverse micelle with IR spectroscopy: a volumetric analysis of the inhomogeneously broadened OH band.

The water OH stretching band (3000-3600 cm(-1)) was analyzed for absorption contributions from the respective bulk and interfacial water regions of a reverse micelle. This analysis was performed by correlating volume changes of these regions to changes in the OH band absorption as the micelle radius grows. The volumetric analysis is based on the well established expanding core-shell model for AOT reverse micelles and yields the dimensions of the water regions and their individual spectral responses in the OH band. The interfacial shell thickness was determined to be 0.45 nm for AOT reverse micelles in i-octane. It was found that each water region absorbs at most frequencies in the OH band; however, absorption on the red side of the OH band is dominated by bulk water, while absorption on the blue side is dominated by interfacial water. The bulk spectral response was found to be more similar to pure water, while the interfacial spectrum is strongly blue-shifted reflecting the weaker hydrogen bonding in this region. AOT reverse micelles with radii in the range 2-4 nm conformed well to the volumetric model. However, it was found that determination of the bulk water spectral response is particularly sensitive to uncertainty in the micelle radius.