Premium
First‐principles calculation of temperature‐dependent electronic transitions mechanism in V or Nb substituted BiFeO 3
Author(s) -
Li Hailong,
Bian Liang,
Dong Faqin,
Song Mianxin,
Li Weimin,
Riehle Frank S.,
Jiang Xiaoqiang,
Lin Yanhui,
Wang Chengxia,
Li Yu,
Luo Weihui
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26041
Subject(s) - atomic orbital , molecular orbital , density functional theory , electronic structure , crystallography , chemistry , charge (physics) , electron , condensed matter physics , electronic correlation , type (biology) , physics , atomic physics , computational chemistry , molecule , quantum mechanics , ecology , organic chemistry , biology
Here, we present a simulation study of temperature‐dependent electronic transitions in BiVO 3 (BVO) and BiNbO 3 (BNO) using density functional theory (DFT) together with generalized gradient approximation (GGA) and two‐dimensional correlation analysis (2D‐CA). The results indicate that heat accumulation can accelerate the degeneracy of V‐3d orbital in BVO and the splitting of Nb‐4d orbital in BNO at 750 K. We found changes in the type of d–p hybrid orbital as follows, for BVO: V‐d x 2 +y 2 + d Z 2 ‐O‐2p z → V‐d x 2 +y 2 ‐O‐2p z ; and for BNO: Nb‐d x 2 +y 2 ‐O‐2p z → Nb‐d x 2 +y 2 + d Z 2 ‐O‐2p z . Furthermore, we found changes in the type of hybrid orbital leading to the following electron–electron interactions, for BVO: t 2g (V‐d Z 2 ‐O‐2p z ) + e g (V‐d x 2 +y 2 ‐O‐2p z ) → t 2g (V‐d x 2 +y 2 ‐O‐2p z ); and for BNO: t 2g + e g (Nb‐d x 2 +y 2 + d Z 2 ‐O‐2p z ) → t 2g (Nb‐d x 2 +y 2 ‐O‐2p z ) + e g (Nb‐d z 2 ‐O‐2p z ). The electronic transitions are determined by a charge‐transfer from the occupied O‐2p 4 orbitals to the unoccupied V‐3d 3 (or Nb‐4d 3 ) and Bi‐6p 3 orbitals. Due to the temperature‐dependent electronic structure closely related to these electronic transitions, this study provides a new perspective for the design and improvement of BFO‐based temperature‐sensitive devices.