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: Marco Verdicchio Applicant's institution: ANL Applicant's division: CSE Project Name: 2DME Project title: 2DME: a priori prediction of pressure-dependent kinetics Associated funding: DOE-BES Other Systems: linus.tcg.anl.gov, pople.tcg.anl.gov Science: The description of the pressure dependence is a key point for the kinetic modeling of combustion and atmospheric processes. The ability to predict pressure-dependent rate parameters would dramatically improve the utility of theoretical kinetics simulations for the modeling of practical chemical problems especially for extreme conditions where the validity of experimental results is questionable. To address this problem, Jasper et al. [1] proposed a new full a priori two-dimensional master equation (2DME) scheme. This approach uses trajectory simulations to predict the collision-induced transitions in the energy, E, and angular momentum, J, thereby overcoming the empiricism and consequent uncertainties arising from the formulation of collisional energy transfer parameters adopted in prior theoretical kinetics studies. Project description: The approach proposed by Jasper et al. consists mainly in two parts: 1) Representation of the collisional energy transfer through an ad-hoc functional form. 2) Calculation of the pressure and temperature dependent kinetics through solution of two-dimensional master equation (2DME). The first part requires the fitting of an ad-hoc functional form to the results of classical trajectories calculations using a Genetic Algorithm. The obtained functional form is then used by the 2DME code to represent the energy transfer kernel required in the master equation. In the second part the 2DME is solved following the procedure proposed by Jeffrey et al. [2]. The numerical solution of the 2DME requires the diagonalization of large matrices. In the actual implementation of the 2DME code both part 1 and 2 run in parallel. The present project aims to improve their performances on a highly parallel computing systems. In particular we intent to improve the matrix diagonalization in the 2DME, at the present done using the lapack function dgesv, implementing in the code more specialized library [3]-[6]. We intent to use the present approach for the calculation of the pressure-dependent kinetics of combustion relevant reactions (H+O2=HO2, CH3+H=CH4, CH2CH+H=CH2CH2) with several bath gasses (Ar,He,H2O,N2). References: [1] A. W. Jasper, K. M. Pelzer, J. A. Miller, E. Kamarchik, L. B. Harding, S. J. Klippenstein, Science, 346 (2014) 1212-1215. [2] S. J. Jeffrey, K. E. Gates, S. C. Smith, J. Phys. Chem., 100 (1996) 7090–7096. [3] Poulson, J.; Marker, B.; van de Geijn, R. A.; Hammond, J. R.; Romero, N. A. ACM Trans. Math. Softw. 2013, 39 (2), 1 [4] Balay, S.; Gropp, W. D. W.; McInnes, L. C. L.; Smith, B. F. B. In Modern Software Tools in Scientific Computing; Arge, E., Bruaset, A. M., Langtangen, H. P., Eds.; Birkhäuser Press, 1997; pp 163–202. [5] Zhang, H.; Smith, B.; Sternberg, M.; Zapol, P. ACM Trans. Math. Softw. 2007, 33 (2), 9. [6] Keceli M.; Zhang, H.; Zapol, P.; Dixon, D.A.; Wagner, A.F. "Shift-and-Invert Parallel Spectral Transformation Eigensolver: Massively Parallel Performance for Density-Functional Based Tight-Binding", (under review in J. Comput. Chem.) Industry partnership: Project URL: Requested allocation: 250000 Q1: 0 Q2: 0 Q3: 0 Q4: 250000 Justification: Storage requirements: The requester has used undetermined amount hours of their initial startup project. In addition to approving an initial amount, please specify a Category and Subcategory for this project. For a list of the current selection of approved categories, please see: https://wiki.lcrc.anl.gov/wiki/Processes/Categories Once the Allocation committee has approved the project, please go to the Project Management page to create it: https://accounts.lcrc.anl.gov/projects.php Thank You, The LCRC Accounts System