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- Title
Europium-doped silicon clusters EuSin (n = 3–11) and their anions: structures, thermochemistry, electron affinities, and magnetic moments.
- Authors
Yang, Jucai; Wang, Jing; Hao, Yanru
- Abstract
The structures, electron affinities, and dissociation energies of EuSin (n = 3–11) and their anions have been examined by means of four hybrid and pure density functional theory (DFT) methods. Basis sets used in this work are of segmented (SEG) Gaussian valence basis sets and relativistic small-core effective core potentials (ECP) with additional diffuse 2pdfg functions, denoted aug-SEG/ECP for Eu atoms and aug-cc-pVTZ for Si atoms. The geometries are fully optimized with each DFT method independently. The ground-state structures for all of these species are found to be substitutional type, which can be regarded as being derived from the ground-state structure of Sin+1 (and/or Sin+1−) by replacing a Si atom with a Eu atom. The theoretical adiabatic electron affinities (AEAs) of EuSin predicted by the four DFT schemes are in excellent agreement with the experimental data, especially the AEAs of TPSSh and B2PLYP. The average absolute deviations from experiment are by 0.10, 0.06, 0.07, and 0.05 eV, and the largest deviations are 0.16, 0.12, 0.18, and 0.10 eV at the B3LYP, TPSSh, PBE, and B2PLYP levels, respectively. The AEA of EuSin (n = 3–11) is less than that of Sin. With the increase in silicon cluster size, the AEA of EuSin may be close to that of Sin, but cannot be larger than that of Sin. The Eu atom acts as an electron donor, and the bonding between Eu and silicon clusters is ionic in nature. The bond between Eu and silicon clusters of neutral EuSin (n = 3–11) is stronger than that of the anions. The total magnetic moments of EuSin/EuSin− (n = 3–11) and the magnetic moments on the Eu atom do not quench, and the total magnetic moments are contributed by Eu atom. The dissociation energies of Eu atom from EuSin and their anions have also been calculated to examine relative stabilities.
- Subjects
THERMOCHEMISTRY; ELECTRON affinity; MAGNETIC moments; ANIONS; DENSITY functional theory; PSEUDOPOTENTIAL method
- Publication
Theoretical Chemistry Accounts: Theory, Computation, & Modeling, 2015, Vol 134, Issue 7, p1
- ISSN
1432-881X
- Publication type
Article
- DOI
10.1007/s00214-015-1684-9