Modeling reactive scattering of F( 2P) at a liquid squalane interface

A hybrid QM/MM molecular dynamics study

Brian K. Radak, Scott Yockel, Dongwook Kim, George C Schatz

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

To better understand the reactivity of gases with liquid surfaces, experimentalists have recently probed the reactive scattering of atomic fluorine at the surface of liquid squalane (C 3oH 62). In this paper we further this research by simulating this scattering process at collision energies of 0.5 and 1.0 eV using a hybrid QM/MM molecular dynamics scheme. To model the structure of the liquid surface, classical molecular dynamics calculations were performed utilizing the OPLS-AA force field. During the F + squalane molecular dynamics simulation, QM/MM calculations are performed at every trajectory step by combining the MSINDO semiempirical Hamiltonian with OPLS-AA and using a dynamic partitioning of the atoms in the QM or MM regions via a "seed atom" method. This computational model provides a type of "on-the-fly" direct dynamics applicable to larger scale chemical processes that include the making/breaking of chemical bonds not available in standard force field models. Our results show that H abstraction is the only reactive scattering pathway and that most trajectories result in reactive scattering. Reaction statistics at the squalane surface are discussed, including variation of the results with incident angle and collision energy, and the probability of reaction as a function of carbon atom type, collision depth, and residence time. Product states, including angular distributions and final translational and rovibrational energies, are also considered and found to be significantly affected by the exothermic reaction energy for H abstraction. The vibrational distributions are in good agreement with recent experiments, but the rotational distributions are dominated by a nonthermal component while the experiments, which involve thermal incident energies, show comparable thermal and nonthermal contributions. Results for O + squalane at 1.0 eV, which we also present, show analogous comparisons with experiment, with OH vibrational distributions which are cold and match experiment, while the calculated rotational distributions are dominated by nonthermal behavior.

Original languageEnglish
Pages (from-to)7218-7226
Number of pages9
JournalJournal of Physical Chemistry A
Volume113
Issue number26
DOIs
Publication statusPublished - Jul 2 2009

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Molecular dynamics
Scattering
molecular dynamics
Liquids
liquids
scattering
Atoms
liquid surfaces
Experiments
Trajectories
field theory (physics)
collisions
Hamiltonians
Exothermic reactions
Fluorine
energy
trajectories
Angular distribution
Chemical bonds
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Modeling reactive scattering of F( 2P) at a liquid squalane interface : A hybrid QM/MM molecular dynamics study. / Radak, Brian K.; Yockel, Scott; Kim, Dongwook; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 113, No. 26, 02.07.2009, p. 7218-7226.

Research output: Contribution to journalArticle

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