Premium
Defect Structures, Electronic Properties, UV–Vis, and EPR Parameters for Rh 2+ Centers in LiD: A DFT Study
Author(s) -
Wu LiNa,
Wu ShaoYi,
Liu XuSheng,
Zhong SiYing,
Zhang Fu
Publication year - 2018
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.201800026
Subject(s) - electron paramagnetic resonance , orthorhombic crystal system , crystallography , tetragonal crystal system , density functional theory , center (category theory) , electronic structure , chemistry , vacancy defect , population , materials science , molecular physics , nuclear magnetic resonance , crystal structure , physics , computational chemistry , demography , sociology
The defect structures and electronic properties of orthorhombic elongated (O E ) and tetragonal compressed (T C ) Rh 2+ centers in LiD are theoretically studied using Density Functional Theory (DFT) with the periodic CP2K program. The calculations demonstrate obvious differences in defect structure between the two centers. O E center with one next nearest neighbor (nnn) cation vacancy (V Li ) in [100] axis shows the Jahn‐Teller elongation of about 0.076 Å along [001] axis, whereas T C center with one nnn V Li in [001] axis exhibits a compression of about 0.049 Å along this direction. The ligand between the central Rh 2+ and the V Li is found to move away from the V Li by about 0.038 or 0.035 Å for O E or T C center. The larger magnitude of the overlap population (≈ −0.5907 or −0.5494 e) of the RhD bonds in O E or T C center than that (≈0.2373 e) of the host LiD bonds in pure LiD indicates much stronger covalency of the former. The simulated UV–Vis and electron paramagnetic resonance (EPR) spectra with the embedded cluster model in ORCA code are consistent with the experimental data. The present results are discussed and compared with those of the previous perturbation calculations.