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Journal article
Mapping spin contamination-free potential energy surfaces using restricted open-shell methods with Grassmannians
Physical chemistry chemical physics : PCCP, Vol.26(2), pp.1436-1442
01/03/2024
PMID: 38113092
Web of Science ID: WOS:001128291900001
Abstract
The Lagrange-based Grassmann interpolation (G-Int) method has been extended for open-shell systems using restricted open-shell (RO) methods. The performance of this method was assessed in constructing potential energy surfaces (PESs) for vanadium(ii) oxide, benzyl radical, and methanesulfenyl chloride radical cation. The density matrices generated by G-Int when used as initial guesses for self-consistent field (SCF) calculations, exhibit superior performance compared to other traditional SCF initial guess schemes, such as SADMO, GWH, and CORE. Additionally, the energy obtained from the G-Int scheme satisfies the variational principle and outperforms the direct energy-based Lagrange interpolation approach. In the case of methanesulfenyl chloride radical cation, a unique example with a flat PES at the end region along the H-C-S-Cl dihedral angle, the use of an equally-spaced grid sampling leads to significant oscillations near the end of the interval due to the effects of Runge's phenomenon. Introducing an unequally-spaced grid sampling based on a scaled Gauss-Chebyshev quadrature effectively mitigated the Runge's phenomenon, making it suitable for combining with G-Int in constructing PESs for general applications. Thus, G-Int provides an efficient and robust strategy for building spin contamination-free PESs with consistent accuracy.
The Lagrange-based Grassmann interpolation (G-Int) method has been extended for open-shell systems using restricted open-shell methods in building spin contamination-free potential energy surfaces.
Details
- Title
- Mapping spin contamination-free potential energy surfaces using restricted open-shell methods with Grassmannians
- Publication Details
- Physical chemistry chemical physics : PCCP, Vol.26(2), pp.1436-1442
- Resource Type
- Journal article
- Publisher
- Royal Society of Chemistry
- Number of pages
- 7
- Grant note
- National Energy Research Scientific Computing CenterVirginia Commonwealth University College of Humanities and SciencesDOE Office of Science User Facility: BES-ERCAP0020838 Office of Science of the U.S. Department of Energy
This work was supported by start-up funds from the Virginia Commonwealth University College of Humanities and Sciences. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231 using NERSC Award No. BES-ERCAP0020838. High Performance Computing resources provided by the High Performance Research Computing (HPRC) Core Facility at Virginia Commonwealth University (https://chipc.vcu.edu) and High Performance Computing (HPC) environment at the University of Richmond were also used for conducting the research reported in this work.
- Identifiers
- WOS:001128291900001; 99381548017006600
- Academic Unit
- Chemistry; Hal Marcus College of Science and Engineering
- Language
- English