期刊
MOLECULAR PHYSICS
卷 114, 期 7-8, 页码 1189-1198出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268976.2015.1123316
关键词
Quantum defect; Rydberg excitation; particle-particle random phase approximation
资金
- Center for the Computational Design of Functional Layered Materials, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0012575]
- U.S Department of Energy ( DOE), Office of Science, Basic Energy Sciences (BES) [DE-FG02-08ER46496]
- National Science Foundation [CHE-1362927]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1362927] Funding Source: National Science Foundation
The accuracy of calculations of atomic Rydberg excitations cannot be judged by the usual measures, such as mean unsigned errors of many transitions. We show how to use quantum defect (QD) theory to (a) separate errors due to approximate ionisation potentials, (b) extract smooth QDs to compare with experiment, and (c) quantify those defects with a few characteristic parameters. The particle-particle random phase approximation (pp-RPA) produces excellent Rydberg transitions that are an order of magnitude more accurate than those of time-dependent density functional theory with standard approximations. We even extract reasonably accurate defects from the lithium Rydberg series, despite the reference being open-shell. Our methodology can be applied to any Rydberg series of excitations with four transitions or more to extract the underlying threshold energy and characteristic QD parameters. Our pp-RPA results set a demanding challenge for other excitation methods to match. [GRAPHICS] .
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