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Bruce C Garrett

Publications and source records attributed to Bruce C Garrett.

11 recordsLinked to original sources
PubMed2006

The OH radical-H2O molecular interaction potential.

The OH radical is one of the most important oxidants in the atmosphere due to its high reactivity. The study of hydrogen-bonded complexes of OH with the water molecules is a topic of significant current interest. In this work, we present the development of a new analytical functional form for the interaction potential between the rigid OH radical and H(2)O molecules. To do this we fit a selected functional form to a set of high level ab initio data. Since there is a low-lying excited state for the H(2)O.OH complex, the impact of the excited state on the chemical behavior of the OH radical can be very important. We perform a potential energy surface scan using the CCSD(T)/aug-cc-pVTZ level of electronic structure theory for both excited and ground states. To model the physics of the unpaired electron in the OH radical, we develop a tensor polarizability generalization of the Thole-type all-atom polarizable rigid potential for the OH radical, which effectively describes the interaction of OH with H(2)O for both ground and excited states. The stationary points of (H(2)O)(n)OH clusters were identified as a benchmark of the potential.

Journal Article↗
PubMed2006

On NO3--H2O interactions in aqueous solutions and at interfaces.

The constrained molecular-dynamics technique was employed to investigate the transport of a nitrate ion across the water liquid/vapor interface. We developed a nitrate-ion-water polarizable potential that accurately reproduces the solvation properties of the hydrated nitrate ion. The computed free-energy profile for the transfer of the nitrate ion across the air/water interface increases monotonically as the nitrate ion approaches the Gibbs dividing surface from the bulk liquid side. The computed density profiles of 1M KNO(3) salt solution indicate that the nitrate and potassium ions are both found below the aqueous interface. Upon analyzing the results, we conclude that the probability of finding the nitrate anion at the aqueous interface is quite small.

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PubMed2006

Sensitivity analysis of thermodynamic properties of liquid water: a general approach to improve empirical potentials.

A sensitivity analysis of bulk water thermodynamics is presented in an effort to understand the relation between qualitative features of molecular potentials and properties that they predict. The analysis is incorporated in molecular dynamics simulations and investigates the sensitivity of the Helmholtz free energy, internal energy, entropy, heat capacity, pressure, thermal pressure coefficient, and static dielectric constant to components of the potential rather than the parameters of a given functional form. The sensitivities of the properties are calculated with respect to the van der Waals repulsive and the attractive parts, plus short- and long-range Coulomb parts of three four site empirical water potentials: TIP4P, Dang-Chang and TTM2R. The polarization sensitivity is calculated for the polarizable Dang-Chang and TTM2R potentials. This new type of analysis allows direct comparisons of the sensitivities for different potentials that use different functional forms. The analysis indicates that all investigated properties are most sensitive to the van der Waals repulsive, the short-range Coulomb and the polarization components of the potentials. When polarization is included in the potentials, the magnitude of the sensitivity of the Helmholtz free energy, internal energy, and entropy with respect to this part of the potential is comparable in magnitude to the other electrostatic components. In addition similarities in trends of observed sensitivities for nonpolarizable and polarizable potentials lead to the conclusion that the complexity of the model is not of critical importance for the calculation of these thermodynamic properties for bulk water. The van der Waals attractive and the long-range Coulomb sensitivities are relatively small for the entropy, heat capacity, thermal pressure coefficient and the static dielectric constant, while small changes in any of the potential contributions will significantly affect the pressure. The analysis suggests a procedure for modification of the potentials to improve predictions of thermodynamic properties and we demonstrate this general approach for modifying potentials for one of the potentials.

Journal Article↗
PubMed2005

Molecular dynamics simulations of atmospheric oxidants at the air-water interface: solvation and accommodation of OH and O3.

A comparative study of OH, O3, and H2O equilibrium aqueous solvation and gas-phase accommodation on liquid water at 300 K is performed using a combination of ab initio calculations and molecular dynamics simulations. Polarizable force fields are developed for the interaction potential of OH and O3 with water. The free energy profiles for transfer of OH and O3 from the gas phase to the bulk liquid exhibit a pronounced minimum at the surface, but no barrier to solvation in the bulk liquid. The calculated surface excess of each oxidant is comparable to calculated and experimental values for short chain, aliphatic alcohols. Driving forces for the surface activity are discussed in terms of the radial distribution functions and dipole orientation distributions for each molecule in the bulk liquid and at the surface. Simulations of OH, O3, and H2O impinging on liquid water with a thermal impact velocity are used to calculate thermal accommodation (S) and mass accommodation (alpha) coefficients. The values of S for OH, O3, and H2O are 0.95, 0.90, and 0.99, respectively. The approaching molecules are accelerated toward the liquid surface when they are approximately 5 angstroms above it. The molecules that reach thermal equilibrium with the surface do so within 2 ps of striking the surface, while those that do not scatter into the gas phase with excess translational kinetic energy in the direction perpendicular to the surface. The time constants for absorption and desorption range from approximately 35 to 140 ps, and the values of alpha for OH, O3, and H2O are 0.83, 0.047, and 0.99, respectively. The results are consistent with previous formulations of gas-phase accommodation from simulations, in which the process occurs by rapid thermal and structural equilibration followed by diffusion on the free energy profile. The implications of these results with respect to atmospheric chemistry are discussed.

Air↗
PubMed2005

Ion-induced nucleation: the importance of chemistry.

Experiments have shown that ions can substantially increase vapor-to-liquid nucleation rates. However, interpretation of these experiments is complicated by ambiguities arising from the manner in which the ions are produced. Several studies have concluded that water has a general preference for anions over cations. We show that specification of the ion's sign alone is insufficient to provide an understanding of the aqueous ionic cluster thermodynamics and that classical ion-induced nucleation theory does not treat the cluster physics properly to describe ion-induced nucleation accurately.

Journal Article↗
PubMed2004

Hydroxyl radical at the air-water interface.

Interaction of the hydroxyl radical with the liquid water surface was studied using classical molecular dynamics computer simulations. From a series of scattering trajectories, the thermal and mass accommodation coefficients of OH on liquid water at 300 K were determined to be 0.95 and 0.83, respectively. The calculated free energy profile for transfer of OH across the air-water interface at 300 K exhibits a minimum in the interfacial region, with the free energy of adsorbtion (DeltaGa) being about 1 kcal/mol more negative than the hydration free energy (DeltaGs). The propensity of the hydroxyl radical for the air-water interface manifests itself in partitioning of OH radicals between the bulk water and the surface. The enhancement of the surface concentration of OH relative to its concentration in the aqueous phase suggests that important OH chemistry may be occurring in the interfacial layer of water droplets, aqueous aerosol particles, and thin water films adsorbed on solid surfaces. This has profound consequences for modeling heterogeneous atmospheric chemical processes.

Air↗
PubMed2004

Multicomponent dynamical nucleation theory and sensitivity analysis.

Vapor to liquid multicomponent nucleation is a dynamical process governed by a delicate interplay between condensation and evaporation. Since the population of the vapor phase is dominated by monomers at reasonable supersaturations, the formation of clusters is governed by monomer association and dissociation reactions. Although there is no intrinsic barrier in the interaction potential along the minimum energy path for the association process, the formation of a cluster is impeded by a free energy barrier. Dynamical nucleation theory provides a framework in which equilibrium evaporation rate constants can be calculated and the corresponding condensation rate constants determined from detailed balance. The nucleation rate can then be obtained by solving the kinetic equations. The rate constants governing the multistep kinetics of multicomponent nucleation including sensitivity analysis and the potential influence of contaminants will be presented and discussed.

Journal Article↗
PubMed2003

H+H2 thermal reaction: a convergence of theory and experiment.

New experimental and theoretical rate constants for two isotopologs of the simplest chemical reaction, H+H2-->H2+H, are presented. The theoretical results are obtained using accurate quantum dynamics with a converged Born-Oppenheimer potential energy surface and include non-Born-Oppenheimer corrections. The new experiments are carried out using a shock tube and complement earlier investigations over a very large T range, 167 to 2112 K. Experiment and theory now agree perfectly, within experimental error, bringing this 75-year-old scientific problem to completion.

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