Ben M. Elliott

How the Shape of an H-Bonded Network Controls Proton-Coupled Water Activation in HONO Formation

Its the Network Numerous reactions of small molecules and ions in the atmosphere take place in the confines of watery aerosols. Relph et al. (p. 308; see the Perspective by Siefermann and Abel) explored the specific influence of a water clusters geometry on the transformation of solvated nitrosonium (NO+) to nitrous acid (HONO). The reaction involves (O)N–O(H) bond formation with one water molecule, concomitant with proton transfer to additional, surrounding water molecules. Vibrational spectroscopy and theoretical simulations suggest that certain arrangements of the surrounding water network are much more effective than others in accommodating this charge transfer, and thus facilitating the reaction. Vibrational spectroscopy uncovers the role of a surrounding water network in the mediating reaction of a solvated ion. Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)–bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

Anharmonicities and isotopic effects in the vibrational spectra of X-.H2O, .HDO, and .D2O [X = Cl, Br, and I] binary complexes.

Vibrational predissociation spectra of the argon-tagged halide monohydrates, X(-) .H(2)O.Ar (X = Cl, Br, or I), are recorded from approximately 800 to 3800 cm(-1) by monitoring the loss of the argon atom. We use this set of spectra to investigate how the spectral signatures of the hydrogen-bonding and large-amplitude hindered rotations of the water molecule are affected by incremental substitution of the hydrogen atoms by deuterium. All six vibrational modes of the X(-).H(2)O complexes are assigned through fundamental transitions, overtones, or combination bands. To complement the experimental study, harmonic and reduced-dimensional calculations of the vibrational spectra are performed based on the MP2/aug-cc-pVTZ level of theory and basis set. Comparison of these results with those from the converged six-dimensional calculations of Rheinecker and Bowman [J. Chem. Phys. 2006, 125, 133206.] show good agreement, with differences smaller than 30 cm(-1). The simpler method has the advantage that it can be readily extended to the heavier halides and was found to accurately recover the wide range of behaviors displayed by this series, including the onset of tunneling between equivalent minima arising from the asymmetrical (single ionic hydrogen-bonded) equilibrium structures of the complexes.

Why Does Argon Bind to Deuterium? Isotope Effects and Structures of Ar·H 5O 2 + Complexes

Recently, we reported the spectrum of Ar x D4HO2(+) [McCunn; et, al. J. Phys. Chem. B 2008, 112, 321], and here, we extend that work to include the Ar x H4DO2(+) isotopologue in order to explore why the Ar atom has a much greater propensity for attachment to a dangling OD group than it does for OH, even when many more of the latter binding sites are available. Calculated (MP2/6-311+G(d,p) level of theory/basis) harmonic frequencies reproduce the observed multiplet patterns of OH and OD stretches and confirm the presence of various isomers arising from the different Ar binding sites. The preferential bonding of Ar to OD is traced to changes in the frequencies of the wag and rock modes of the H5O2(+) moiety rather than to shifts in the oscillator that directly binds the Ar atom.

High resolution spectral analysis of oxygen. III. Laboratory investigation of the airglow bands

We report the first high spectral resolution laboratory measurements of simulated oxygen A-band night glow. Our static discharge system approximates the conditions of the mesospheric oxygen night glow--suggesting O((1)D) + O2 (X(3)Σg(-)) → O((3)P) + O2 (b(1)Σg(+)) → O2 (X(3)Σg(-)) + hν as the primary source of the emission. Additionally, use of the static cell has enabled us to collect spectra for all six molecular oxygen isotopologues using isotopically enriched samples. The (0,0), (0,1), and (1,1) b - X vibrational bands were observed for all six isotopologues. The (1,2) and (2,2) bands were also observed for (16)O2. The frequencies of the observed (0,1) transitions resolved discrepancies in Raman data for (16)O(17)O, (17)O2, and (17)O(18)O, enabling us to improve the vibrational parameterization of the ground electronic state global fit. Rotationally resolved intensities were determined for the (0,0), (0,1), and (1,1) bands. The experimental band intensity ratios I(0,0)/I(0,1) = 13.53(24); I(1,1)/I(1,0) = 11.9(65); I(0,0)/I(0,2) = 503(197); and I(1,1)/I(1,2) = 5.6(19) are in excellent agreement with the recent mesospheric remote sensing data and calculated Franck-Condon factors.

Vibrationally Induced Interconversion of H-Bonded NO2−·H2O Isomers within NO2−·H2O·Arm Clusters Using IR−IR Pump−Probe through the OH and NO Stretching Vibrations

We introduce a method based on sequential application of vibrational predissociation spectroscopy to explore the high-amplitude rearrangements available in a small H-bonded complex that is vibrationally excited within a larger Ar cluster. The weakly bound Ar atoms play the role of a solvent in mediating the energy content of the embedded system, ultimately quenching it into local minima through evaporation. We demonstrate the approach on the NO(2)(-) x H(2)O binary hydrate, which is known to occur in two nearly isoenergetic isomeric forms. The scheme involves three stages of mass separation to select a particular NO(2)(-) x H(2)O x Ar(m) parent ion cluster prior to vibrational excitation and then isolate the NO(2)(-) x H(2)O x Ar fragment ions for interrogation using resonant vibrational predissociation with a second infrared laser. The initial vibrational excitation selectively energizes one of the isomers through one of its characteristic resonances while the predissociation spectrum of the NO(2)(-) x H(2)O x Ar fragment encodes the distribution of isomers present after Ar evaporation. Isomerization from the front- to backside form is found to occur upon excitation of the NO stretch near 1200 cm(-1); although the reverse reaction is not observed upon excitation of the NO stretch, it is observed upon excitation of the higher-energy OH stretching fundamental near 3000 cm(-1). We discuss these observations in the context of the calculated isomerization energetics, which focus on the minimum energy structures for the isomers as well as the transition states for their interconversion.