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Real-Space Pseudopotential Method for the Calculation of Third-Row Elements X-ray Photoelectron Spectroscopic Signatures

Journal Article · · Journal of Chemical Theory and Computation
X-ray photoelectron spectroscopy (XPS) is a powerful characterization technique that unveils subtle chemical environment differences via core– electron binding energy (CEBE) analysis. We extend the development of realspace pseudopotential methods to calculating 1s, 2s, and 2p3/2 CEBEs of third-row elements (S, P, and Si) within the framework of Kohn–Sham density-functional theory (KS-DFT). The new approach systematically prevents variational collapse and simplifies core-excited orbital selection within dense energy level distributions. However, careful error cancellation analysis is required to achieve accuracy comparable to all-electron methods and experiments. Combined with real-space KS-DFT implementation, this development enables large-scale simulations with both Dirichlet boundary conditions and periodic boundary conditions.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231; SC0021266
OSTI ID:
2395988
Alternate ID(s):
OSTI ID: 2406184
OSTI ID: 2568336
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 14 Vol. 20; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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