New energetic ionic liquids are investigated as potential high energy density materials. Ionic liquids are composed of large, charge-diffuse cations, coupled with various (usually oxygen containing) anions. In this work, calculations have been performed on the tetrazolium cation with a variety of substituents. Density functional theory (DFT) with the B3LYP functional, using the 6-311G(d,p) basis set was used to optimize geometries. Improved treatment of dynamic electron correlation was obtained using second-order perturbation theory (MP2). Heats of formation of the cation with different substituent groups were calculated using isodesmic reactions and Gaussian-2 calculations on the reactants. The cation was paired with oxygen rich anions ClO4-, NO3-, or N(NO2)2-and those structures were optimized using both DFT and MP2. The reaction pathway for proton transfer from the cation to the anion was investigated. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: February 9, 2006; In Final Form: April 3, 2006 New energetic ionic liquids are investigated as potential high energy density materials. Ionic liquids are composed of large, charge-diffuse cations, coupled with various (usually oxygen containing) anions. In this work, calculations have been performed on the tetrazolium cation with a variety of substituents. Density functional theory (DFT) with the B3LYP functional, using the 6-311G(d,p) basis set was used to optimize geometries. Improved treatment of dynamic electron correlation was obtained using second-order perturbation theory (MP2). Heats of formation of the cation with different substituent groups were calculated using isodesmic reactions and Gaussian-2 calculations on the reactants. The cation was paired with oxygen rich anions ClO 4 -, NO 3 -, or N(NO 2 ) 2 -and those structures were optimized using both DFT and MP2. The reaction pathway for proton transfer from the cation to the anion was investigated.
Deposition at room temperature of Ga on Si(100) produces single-atom-wide metal rows orthogonal to the Si-dimer rows. Detailed analysis using scanning tunneling microscopy reveals a monotonically decreasing size (i.e., length) distribution for these rows. This is unexpected for homogeneous nucleation without desorption, conditions which are operative in this system. Kinetic Monte Carlo simulation of an appropriate atomistic model indicates that this behavior is primarily a consequence of the feature that the capture of diffusing atoms is greatly inhibited in the Ga∕Si(100) system. The modeling also determines activation barriers for anisotropic terrace diffusion, and recovers the experimental distribution of metal rows. In addition, we analyze a variety of other generic deposition models and determine that the propensity for a large population of small islands in general reflects an enhanced nucleation rate relative to the aggregation rate. Disciplines Chemistry CommentsThis article is from Physical Review B 72 (2005) Deposition at room temperature of Ga on Si͑100͒ produces single-atom-wide metal rows orthogonal to the Si-dimer rows. Detailed analysis using scanning tunneling microscopy reveals a monotonically decreasing size ͑i.e., length͒ distribution for these rows. This is unexpected for homogeneous nucleation without desorption, conditions which are operative in this system. Kinetic Monte Carlo simulation of an appropriate atomistic model indicates that this behavior is primarily a consequence of the feature that the capture of diffusing atoms is greatly inhibited in the Ga/ Si͑100͒ system. The modeling also determines activation barriers for anisotropic terrace diffusion, and recovers the experimental distribution of metal rows. In addition, we analyze a variety of other generic deposition models and determine that the propensity for a large population of small islands in general reflects an enhanced nucleation rate relative to the aggregation rate.
When group III metals are deposited onto the Si(100)-2 × 1 reconstructed surface they are observed to selfassemble into chains of atoms that are one atom high by one atom wide. To better understand this onedimensional island growth, ab initio electronic structure calculations on the structures of Al atoms on silicon clusters have been performed. Natural orbital occupation numbers show that these systems display significant diradical character, suggesting that a multireference method is needed. A multiconfiguration self-consistent field (MCSCF) calculation with a 6-31G(d) basis set and effective core potentials was used to optimize geometries. The surface integrated molecular orbital molecular mechanics embedded cluster method was used to take the surface chemistry into account, as well as the structure of an extended surface region. Potential energy surfaces for binding of Al adatoms and Al−Al dimers on the surface were determined, and the former was used to obtain a preliminary assessment of the surface diffusion of adatoms. Hessians were calculated to characterize stationary points, and improved treatment of dynamic electron correlation was accomplished using multireference second order perturbation theory (MRMP2) single-point energy calculations. Results from the MRMP2//MCSCF embedded cluster calculations are compared with those from QM-only cluster calculations, embedded cluster unrestricted density functional theory calculations, and previous Car−Parrinello DFT studies.
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