Grant 30K, Pri 3, P:Chem, Curtiss On Tue, Feb 15, 2011 at 10:23:40AM -0600, [email protected] wrote:
Hello,
A new project on the LCRC cluster has been requested. Please forward the information on to the LCRC Allocation sub-committee.
Applicant's name: Amit Sharma Applicant's institution: ANL Applicant's division: CSE Project Name: HPCC Project title: Ab-initio chemical kinetics study of high pressure combustion: A theoretical study of the radical-complex mechanism. Associated funding: Department of Energy Other Systems: A small cluster (named: Pople) in the CSE fundamental interaction theory group. Science: Recent experimental studies of the falloff curve of the radical-radical association reaction show an unexpected additional rise of the rate constants at pressures above 300 bar in the 300 to 400 K temperature range. Contribution from the radical-complex (RC) mechanism, in addition to the usual energy-transfer (ET) mechanism, is believed to be the dominant factor for this phenomena. The radical-complex mechanism, which has not been theoretically studied and quantified, is the formation of the radical-bath gas (R-M) complex and the stabilization/complexation is related to the strength of the R-M bond in the van der Waals complexes. The decomposition of these R-M complex to stabilized reactants yields an increase in the net association rate.
We propose to study the radical-complex mechanism using high level ab-initio kinetics approach and first principle electronic structure methods. The theoretical/computational approach involves development of a reduced dimensional, semi-global, potential energy surface (PES). This PES development is a novel approach due to high-dimensionality of the molecular system under study. For example, a simple oxidation reaction of CH3 with O2 in a monoatomic bath gas is a 15 dimensional system. The PES is developed by fitting high-level electronic structure energies for the radical-radical addition channel and R-M molecular system.The rate constant for the association reaction is calculated using variable reaction coordinate-transition state theory (VRC-TST) for different bath gas species. Project description: The computational methods used for the electronic structure calculations are available in codes like Molpro, Gaussian and similar quantum chemistry packages. The VRC-TST code is developed within our group. The size of calculations, typically, is about 40,000 to 50,000 electronic structure calculations for each system. The computational cost of each electronic calculation depend on the size of the basis set, electronic structure methods and other auxiliary routines. This can vary anywhere between 0.5 hours to couple of hours for a single electronic structure calculation, for the system we propose to study. There will be 3 to 4 people working on this project who will be using the computational resources. About 30-40% of the allocation will use non-parallel computations.
This work is part of Combustion EFRC. Please see this web link for a brief overview. http://www.princeton.edu/cefrc/ Project URL: Requested allocation: 200000 Justification:
The requester has used 0 hours of their initial startup project.
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