Molecular dynamics simulation of hydrochloric acid ionization at the surface of stratospheric ice

Science

Volumn 271, Issue 5255, 1996, Pages 1563-1566

  Gertner, Bradley J ^a   Hynes, James T ^a  

^a UNIVERSITY OF COLORADO   (United States)

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EID: 0001183787     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.271.5255.1563     Document Type: Article

References (55)

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34. J. Mol. Liq. 64, 25 (1995); in preparation. The ΔG of HCI lonization in liquid water calculated for the CIP is -6.7 kcal/mol, and the overall experimental reaction ΔG is roughly -8 to -10 kcal/rnol. With an estimated additional stabilization at infinite separation of less than 1 kcal/ mol, the former is a numerically reasonable estimate for the aqueous lonization
35. T = 0.43, respectively.
36. T = 0.43, respectively.
37. +.
38. O, from both states, for example, the reactant and product states.
39. We implemented the method (19) stepwise, so that the ΔE distributions from each state had significant overlap (the large sample regime). This required five intermediate states between reactants and products (seven total), each state generated as a linear combination of the molecular and ionic states. The resultant ΔG estimate is the sum of the intermediate estimates (19) The sequence of (fixed) intermediate states with equilibrated solvent closely resembles an equilibrium soivation reaction path in ΔE [see (16) and J. Juanós i Timoneda and J. T Hynes, J. Phys. Chem. 95, 10431 (1991)].
40. 2O dinner as 34.7 kcal/mol. Using the data in (76), we estimated the zero-point energy change at a CIP destabilization of 1 6 kcal/mol. The net correction was 36.3 kcal/mol. The five intermediate-state energies were linearly interpolated between those of the MP and CIP states.
41. Rigid body rotational molecular motions were implemented with quaternions (12) in a Hamiltonian representation (13) The Verlet algorithm (12) was used to integrate Hamilton's equations (6.25-fs time step). Because the system is anisotropic, special semi-infinite periodic boundary conditions have been developed (13) to handle the long-range Coulombic interactions: (i) an accelerated two-dimensional Ewald sum technique that eliminates convergence problems [J. Hautman and M. L. Klein, Mol. Phys 75, 379 (1992)], (II) a dielectric continuum representation of the bulk ice tying below the sample but not explicitly evaluated in the simulation; and (iii) a hexagonal box to minimize cubic boundary condition artifacts and to maximize solute-solvent interaction efficiency The boundary conditions allowed system size reduction without significant truncation errors or convergence problems. The periodic image of the HCI molecule is approximately 15 Å from the original HCI. For the CIP, there will be significant image screening in the ice that has a high dielectric constant Because the simulations were used only for equilibrium properties, all protons were replaced by deuterons to improve numerical accuracy and computational efficiency
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43. To reduce the effects of spurious, large interaction forces due to solute insertion, we integrated the first picosecond, using the following scheme. For the first 50 fs, the integration step was set at 1 25 fs, and the momenta were randomized every 5 fs, For the next 150 fs, they were set at 2.5 fs and 10 fs. For the remaining 800 fs we used an integration step of 5 fs, with randomizations every 10 fs
44. We ran 28 trajectories per case, representing a total simuiation time of 9.52 ns, using 290 central processing unit (CPU) hours on an IRM/RS6000 model 590 computer (5 6 ns) and anothor 650 CPU hours on an Apple Power Macintosh 7100/82 computer (3 92 ns). Increasing equilibration times above 70 ps (and thus decreasing data collection times below 100 ps) showed no significant difference.
45. S. C Colbeck, J. Cryst Growth 72, 726 (1985). Although temperatures above 253 K were dealt with, no change in behavior below 263 K was reported. The relative surface area of the basal-plane faces was somewhat greater than that of the prism faces below 263 K. Thus, the basal-plane face is expected to be more relevant at 190 K.
46. The thermodynamics of the various configurations have not been investigated. We addressed here only HCI additions to the second bilayer, which we believe are likely made during the barnerless adsorption process Stable additions to the uppermost bilayer are also possible, as part of bilayer formation or as a result of the replacement of existing waters; however, we believe both of these are activated processes and thus did not consider upper monolayer sites in this first investigation.
47. T- = 0.69 for the CIP products.
48. We inferred above from experiment (7) that these sites represent the majority of HCI available for reaction on the basal-plane face. For completeness, the remaining HCI atop the surface will need to be examined in tho future (along with the prism face and surface defects) After this work was completed, we became aware of the work of S. H. Robertson and D. C. Clary, Faraday Discuss. Ghem Soc., in press. The authors suggest that HCI ionization is energetically favorable from the adsorption site atop the ice surface identified in (14). However, these calculations did not establish that the free energy of the CIP in its equilibrated ice surroundings is lower than the corresponding quantity for the MP.
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50. L. A. Barrie, in The Tropospheric Chemistry of Ozone in the Polar Regions, H. Niki and K H Becker, Eds. (Springer-Verlag, New York, 1993), pp. 3-24.
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52. 6 at 140 K, reported by J. D. Graham and J. T. Roberts [J. Phys. Chem. 98, 5974 (1994)] An HCI with two hydrogen bonds would not be expected to ionize [see (16) and M. J. Packer and D C. Clary, J. Phys Chem. 99, 14323 (1995)]
53. 6 at 140 K, reported by J. D. Graham and J. T. Roberts [J. Phys. Chem. 98, 5974 (1994)] An HCI with two hydrogen bonds would not be expected to ionize [see (16) and M. J. Packer and D C. Clary, J. Phys Chem. 99, 14323 (1995)]
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55. We thank K. Ando for assistance with the electronic structure calculations and gratefully acknowledge useful conversations with R Bianco, S. M. George, A R. Ravishankara, J. T. Roberts, M. A. Tolbert, and V Vaida This work was supported in part by a grant from the Petroleum Research Fund, administered by the American Chemical Society, by National Science Foundation grant CHE 93-12267, and by a special Scientific Computing Division grant for supercomputer time from the National Center for Atmospheric Research