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: Kah Chun Lau Applicant's institution: ANL Applicant's division: MSD Project Name: DFT_electrolytes Project title: Atomistic Simulation of Complex Electrolytes Associated funding: DOE-EERE, DOE-JCESR Other Systems: Science: Electrolytes is a fundamental building block in today's battery research (e.g. Li-ion or beyond Li-ion battery) and developments. Without a systematic study of electrolytes at the atomistic and molecular level, the intelligent design of novel electrolytes cannot not be achieved. For liquid electrolytes, its high flexibility against solid electrolytes in terms of contact interfaces is critically important in terms of real applications. Relative to crystalline solid that can be well-described through the periodic lattices based on DFT calculations, a DFT based simulation of liquid electrolytes are challenging yet rewarding. However, based on a systematic DFT and MD simulation, a basic understanding of molecular and the useful chemical description of the important solvation structures in liquid electrolytes can be obtained. The fundamental knowledges of design rule (e.g. solvation structure determined by functionalized solvents) for a mixed or heteroge neous liquid electrolyte that span across dilute to concentrated regimes [1,2] can be attained based on this theoretical approach. In this proposal, a basic understanding at the atomistic level (e.g. chemical bonding, solvation, vibration features, etc.) of a heterogeneous liquid electrolyte will continue be addressed and explored based on state-of-the-art ab initio atomistic modeling techniques that work closely with experimental colleagues at ANL (funded by DOE-EERE), and experimental collaborators UIC and Ohio State University (OSU) in advanced battery research program. Project description: In the coming fiscal year (FY2017), the computational methods will involve largely AIMD (CPMD, VASP), Quantum Chemistry method (Gaussian09), and classical MD simulation (LAMMPS). To initiate the project, we will need 150, 000 core-hour to model our liquid electrolytes (i.e. mixed LiTFSI@DMSO/IL (with IL is the ionic liquid) at two given salt concentration ratio that determined by experiment based on classical MD simulation. The system size will typically consist of few hundreds solvent molecules in a 36 Å x 36 Å x 36 Å simulation cell. Based on this approach, a reasonable thermodynamic equilibrated sampling of a heterogeneous liquid electrolytes configurations can be obtained. Based on the solvated complexes obtained from classical MD simulation, the thermal equilibrated configurations (from classical MD) will be further downsize into smaller simulation cell (e.g. 16 Å x 16 Å x 16 Å) to be investigated based on Ab Initio MD (AIMD) method based on CPMD and VASP code. Based on AIMD simulation, the detailed electronic properties of the bulk solvated complexes will be studied. In this case, we will need 300, 000 core-hour to complete the study of both dilute and concentrated solution in a given mixed heterogeneous electrolyte. For Gaussian09, the DFT calculation scales well up to 8-16 processors and for 4-6 nodes is the optimal number of nodes for geometry optimization for system size below 100 atoms. We will require about 150,000 core hours to study the underlying electronic properties trend (HOMO-LUMO, charge and spin population, etc.), thermochemistry and vibration (IR/Raman) spectra of the underlying solvated complexes cluster configurations (e.g. (LiTFSI)x(DMSO)y(IL)z with x,y,z = 1-4) obtained from AIMD simulation. For a few cases, more detailed quantum chemistry studies of chemical reactions that involve impurities (e.g. H2O, CO2) will be studied, in parallel with experimental characterizations provided by our experimental colleagues at ANL and UIC. In conclusion, this will need 600 000 core-hour to complete all these proposed problems in FY2017. References: (1) M. He, K.C. Lau, X. Ren, N. Xiao, W. McCulloch, L.A. Curtiss, Y. Wu, Angew Chem (in review). (2). K. See, H. Wu, K.C. Lau, M. Shin, L. Cheng, K. Gallagher, L.A. Curtiss, A. A. Gewirth, ACS Applied Mater. Interface (submitted). Industry partnership: Project URL: Requested allocation: 600000 Q1: 150000 Q2: 150000 Q3: 150000 Q4: 150000 Justification: Further details of the scaling and the performance of the codes can be found as follows: (1) VASP: http://cms.mpi.univie.ac.at/vasp/vasp/Performance_parallel_code_on_various_m... (2) CPMD: http://cpmd.org/documentation (3) Gaussian09: http://www.gaussian.com/g_prod/g09_glance.htm 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