Adaptively Compressed Exchange Operator for Large-Scale Hybrid Density Functional Calculations with Applications to the Adsorption of Water on Silicene
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division ; Univ. of California, Berkeley, CA (United States). Department of Mathematics
Density functional theory (DFT) calculations using hybrid exchange-correlation functionals have been shown to provide an accurate description of the electronic structures of nanosystems. However, such calculations are often limited to small system sizes due to the high computational cost associated with the construction and application of the Hartree-Fock (HF) exchange operator. Here, we demonstrate that the recently developed adaptively compressed exchange (ACE) operator formulation [J. Chem. Theory Comput. 2016, 12, 2242-2249] can enable hybrid functional DFT calculations for nanosystems with thousands of atoms. The cost of constructing the ACE operator is the same as that of applying the exchange operator to the occupied orbitals once, while the cost of applying the Hamiltonian operator with a hybrid functional (after construction of the ACE operator) is only marginally higher than that associated with applying a Hamiltonian constructed from local and semilocal exchange-correlation functionals. Therefore, this new development significantly lowers the computational barrier for using hybrid functionals in large-scale DFT calculations. We demonstrate that a parallel planewave implementation of this method can be used to compute the ground-state electronic structure of a 1000-atom bulk silicon system in less than 30 wall clock minutes and that this method scales beyond 8000 computational cores for a bulk silicon system containing about 4000 atoms. The efficiency of the present methodology in treating large systems enables us to investigate adsorption properties of water molecules on Ag-supported two-dimensional silicene. Our computational results show that water monomer, dimer, and trimer configurations exhibit distinct adsorption behaviors on silicene. In particular, the presence of additional water molecules in the dimer and trimer configurations induces a transition from physisorption to chemisorption, followed by dissociation on Ag-supported silicene. This is caused by the enhanced effect of hydrogen bonds on charge transfer and proton transfer processes. Lastly, such a hydrogen bond autocatalytic effect is expected to have broad applications for silicene as an efficient surface catalyst for oxygen reduction reactions and water dissociation.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
- Grant/Contract Number:
- AC02-05CH11231
- OSTI ID:
- 1456970
- Journal Information:
- Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 3 Vol. 13; ISSN 1549-9618
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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journal | December 2019 |
Speeding-up ab initio molecular dynamics with hybrid functionals using adaptively compressed exchange operator based multiple timestepping
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journal | October 2019 |
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