Ephraim Woods

Reactions of O, H, and Cl atoms with highly vibrationally excited HCN: Using product states to determine mechanisms

Oxygen, hydrogen, and chlorine atoms react with vibrationally excited HCN to produce CN and OH, H2, or HCl, respectively. The experiments presented here use direct vibrational overtone excitation to prepare states of HCN having four quanta of C–H stretching excitation [(004) state] or three quanta of C≡N stretching and two quanta of C–H stretching excitation [(302) state] and laser‐induced fluorescence to determine the rotational and vibrational states of the CN product. We find that the reaction of HCN with O produces CN having little vibrational and rotational energy, with 85% of the CN in v=0, 12% in v=1, and 3% in v=2. The CN from the reaction of H with HCN is slightly more energetic, with 77% in v=0, 17% in v=1, and 6% in v=2. By contrast, the reaction of Cl with HCN produces CN with a considerable amount of excitation, about 30% is in v=1 and at least 10% is in v=2, depending on the initial vibrational state of the HCN reactant. The enhanced excitation of the CN product of the reaction with Cl refle...

Vibrational spectroscopy and intramolecular energy transfer in isocyanic acid (HNCO)

Room temperature photoacoustic spectra in the region of the first through the fourth overtones (2ν1 to 5ν1) and free-jet action spectra of the second through the fourth overtones (3ν1 to 5ν1) of the N–H stretching vibration permit analysis of the vibrational and rotational structure of HNCO. The analysis identifies the strong intramolecular couplings that control the early stages of intramolecular vibrational energy redistribution (IVR) and gives the interaction matrix elements between the zero-order N–H stretching states and the other zero-order states with which they interact. The experimentally determined couplings and zero-order state separations are consistent with ab initio calculations of East, Johnson, and Allen [J. Chem. Phys. 98, 1299 (1993)], and comparison with the calculation identifies the coupled states and likely interactions. The states most strongly coupled to the pure N–H stretching zero-order states are ones with a quantum of N–H stretching excitation (ν1) replaced by different combina...

Probing the new bond in the vibrationally controlled bimolecular reaction of O with HOD(4νOH)

Previous studies of the hydrogen abstraction from vibrationally excited H2O and HCN by various atoms have probed the vibrational and rotational energy of the product containing the surviving bond to assess the energy disposal and determine the mechanism of the reaction. Estimating the relative translational energy of the products from the Doppler broadening of the probe transitions has allowed the inference of the internal energy of the unobserved product containing the new bond using conservation of energy. The experiments presented here directly measure the vibrational and rotational energy of both the OH product (containing the new bond) and OD product (containing the old bond) from the reaction of O atoms with HOD having four quanta of O–H stretching excitation (4νOH). All of the OH products are vibrationally excited, being formed almost exclusively in ν=2. Nearly all of the OD products are vibrationally unexcited, with 93% in v=0 and only 7% in v=1. The results are consistent with a spectator picture...

Surface morphology and phase transitions in mixed NaCl/MgSO4 aerosol particles.

Probe molecule spectroscopy characterizes the surface environment of mixed NaCl/MgSO(4) (0.01-50 wt % MgSO(4)) aerosol particles as a model for marine aerosol. Two complementary measurements, the probes excited state spectroscopy and photoionization efficiency, measure the electronic properties of the particle surface and monitor phase changes that are driven by changes in relative humidity (RH). The results illustrate that over a wide range of composition, these particles have a layered structure with NaCl in the core and primarily hydrated MgSO(4) at the surface. Modeling the spectroscopic data reveals that the surface layer is not a uniform shell and that the coumarin 314 probe molecules partition selectively to the MgSO(4) domains. The surface layer has a pi* value of 1.7, indicative of a very high interfacial polarity. In cases where MgSO(4) is a minor component (< or = 10 wt %), the NaCl component crystallizes at 44% RH, consistent with the single salt NaCl result. Deliquescence-mode experiments with these particles show that the MgSO(4) component forms a solution at 42% RH, prior to the full deliquescence of the particle. For mixed particles with 50 wt % MgSO(4), the crystallization of NaCl occurs at 35% RH, and the predeliquescence of MgSO(4) occurs at 38% RH owing to the contribution of MgCl(2) in the surface layer. A model surfactant, SDS, slightly lowers the RH of the NaCl formation to approximately 42% and leads to the formation of a thin soap film that persists to low values of RH.

Using stretching and bending vibrations to direct the reaction of Cl atoms with isocyanic acid (HNCO)

Reaction of well-characterized vibrational states prepared in the region of three quanta of N–H stretching excitation explores how vibrations with different components along the reaction coordinate influence the bimolecular reaction of Cl atoms with isocyanic acid (HNCO) to form HCl and NCO. Near prolate symmetric top states corresponding to different amounts of a-axis rotation are well separated in energy, and perturbations by background states make each of the eigenstates a different mixture of zero-order states. Molecules in the essentially unperturbed K=1 and 4 states, which are nearly pure N–H stretching excitation, react efficiently, but those in the perturbed states, K=0, 2, and 3, which are a mixture of N–H stretching and lower frequency vibrations react only half as well. Detailed analysis of resolved, perturbed eigenstates for J=6 and 7 of K=3 reveals the relative reactivity of the two interacting zero-order states. The less reactive zero-order state, which most likely contains only two quanta o...

Effects of NOy Aging on the Dehydration Dynamics of Model Sea Spray Aerosol

The reactions of NO(y) species in the atmosphere with sea spray aerosol replace halogen anions with nitrate. These experiments show the effect of increasing the nitrate content of model sea spray aerosol particles on the morphology changes and the phase transitions driven by changes in relative humidity (RH). The components of the model particles include H2O, Na+, Mg2+, Cl-, NO3-, and SO4(2-). Tandem differential mobility analyzer (TDMA) measurements yield the water content and efflorescence relative humidity (ERH) of these particles, and probe molecule spectroscopic measurements reveal subsequent phase transitions and partially characterize the salt composition on the surface of dry particles. The results show three effects of increasing the nitrate composition: decreasing the EFH (46 to 29%), production of a metastable aqueous layer on the surface of effloresced particles, and decreasing the sulfate content near the surface of dry particles. For the mixtures studied here, the initial crystallization event forms a core of NaCl. For particles that contain a substantial metastable aqueous layer following efflorescence, probe molecule spectroscopy shows a second crystallization at a lower RH. This subsequent phase transition is likely the formation of Na2SO4. Homogeneous nucleation theory (HNT) using a semiempirical formulation predicts the ERH of all mixtures within 2.0% RH, with a mean absolute deviation of 1.0%. The calculations suggest that structures associated with highly concentrated or supersaturated magnesium ions strongly affect the interfacial tension between the NaCl crystal nucleus and the droplet from which it forms.

Uptake of pyrene by NaCl, NaNO3, and MgCl2 aerosol particles.

Photoelectric charging experiments measure heterogeneous uptake coefficients for pyrene on model marine aerosol particles, including NaCl, NaNO(3), and MgCl(2). The analysis employs a multilayer kinetic model that contains adsorption and desorption rate constants for the bare aerosol surface and for pyrene-coated surfaces. First coating the aerosol particles with a pyrene layer and following the desorption using both t-DMA and photoelectric charging yields the desorption rate constants. Separate experiments monitor the increase in surface coverage of initially bare aerosol particles after exposure to pyrene vapor in a sliding-injector flow tube. Analyzing these data using the multilayer model constrained by the measured desorption rate constants yields the adsorption rate constants. The calculated initial heterogeneous uptake coefficient, γ(0)(295 K), is 1.1 × 10(-3) for NaCl, 6.6 × 10(-4) for NaNO(3), and 6.0 × 10(-4) for MgCl(2). The results suggest that a free energy barrier controls the uptake rate rather than kinematics.

Uptake of Pyrene onto Fatty Acid Coated NaCl Aerosol Particles

Photoelectric charging experiments monitor the uptake of pyrene onto NaCl aerosol particles coated with either oleic acid or myristic acid. In both cases, thin coatings produce a small net decrease in pyrene uptake. In the larger coverage limit, the uptake of the myristic acid coated particles remains nearly constant whereas the oleic acid coated particles exhibit greater uptake rates than the bare NaCl particles. Fitting the results with a multilayer kinetic model yields uptake rate coefficients as well as parameters that describe the distribution of organic molecules on the aerosol particle surface. The model accounts for the decrease in uptake associated with thin coatings of oleic acid through a concomitant reduction in surface area. The adsorption rate constants for the myristic and oleic acid coated surfaces are 50 and 80 times faster, respectively, than for NaCl. The desorption rates for pyrene on the fatty acid surfaces are faster, as well. For myristic acid coatings, the fast desorption (over 400 times the rate of desorption from NaCl) results in slower net adsorption, whereas for oleic acid (approximately 12 times the desorption rate from NaCl), the net uptake rate increases with coverage. The results also suggest that both myristic acid and oleic acid spread incompletely on the aerosol surfaces under the conditions of these experiments. In the optimized kinetic model, the fatty acids cover approximately 50% of the surface when the nominal coating thickness is approximately 6 nm. The surface is over 90% covered with a nominal coating thickness of 20 nm, which is approximately 10% of particle diameter in these experiments. Very thin oleic acid coatings reduce the surface area of particles consistent with the preferential coverage of highly corrugated or porous regions.

Spectators and Participants in Vibrational State Controlled Bimolecular Reactions

Vibrational excitation provides a means for identifying the degrees of freedom in a molecule that are spectators or participants in a bimolecular reaction. In our study of the reactions of vibrationally excited H2O with H and Cl atoms and vibrationally excited HCN with H, O, and Cl atoms, we find that in direct reactions the nonreacting bond of a molecule is a spectator to the reaction. When the nonreacting bond participates in the reaction, the reaction mechanism is not direct but proceeds through an intermediate complex.