Fabien Pascale, Philippe D'Arco, Sami Mustapha, Roberto Dovesi
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The numerous patterns are distributed into 162 classes of equivalent configurations. For each fluoroperovskite, one representative per class has been calculated. The four compounds behave similarly: an identical dependence of the energy and volume (or cell parameters) on the OO pattern; the spanned energy interval is small (1 to 2 mE<span></span><math>\n <mrow>\n <msub>\n <mrow></mrow>\n <mrow>\n <mi>h</mi>\n </mrow>\n </msub>\n </mrow></math> per formula unit), suggesting that most of the configurations are occupied at room and even at low temperature. A linear model, taking into account the relative orbital order in contiguous sites, reproduces the energy order in the full set for each compound, suggesting that it could be used for studying OO in larger supercells.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":null,"pages":null},"PeriodicalIF":3.4000,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"t\\n \\n \\n 2\\n g\\n \\n \\n \\n \\n d\\n orbital ordering patterns in KBF\\n \\n \\n \\n \\n 3\\n \\n \\n (B = Sc, Ti, Fe, Co) perovskites\",\"authors\":\"Fabien Pascale, Philippe D'Arco, Sami Mustapha, Roberto Dovesi\",\"doi\":\"10.1002/jcc.27391\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The orbital ordering (OO) resulting from the partial occupancy of the <span></span><math>\\n <mrow>\\n <msub>\\n <mrow>\\n <mi>t</mi>\\n </mrow>\\n <mrow>\\n <mn>2</mn>\\n <mi>g</mi>\\n </mrow>\\n </msub>\\n </mrow></math> <span></span><math>\\n <mrow>\\n <mi>d</mi>\\n </mrow></math> subshell of the transition metals in KBF<span></span><math>\\n <mrow>\\n <msub>\\n <mrow></mrow>\\n <mrow>\\n <mn>3</mn>\\n </mrow>\\n </msub>\\n </mrow></math> (B = Sc, Ti, Ffe, Co) perovskites, and the many possible patterns arising from the coupling between the B sites, have been investigated at the quantum mechanical level (<span></span><math>\\n <mrow>\\n <mtext>all electron</mtext>\\n </mrow></math> Gaussian type basis set, B3LYP hybrid functional) in a 40 atoms supercell. 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引用次数: 0
摘要
KBF 3 $$ {}_3 $$ (B = Sc、Ti、Ffe、Co)包晶石中过渡金属的 t 2 g $$ {t}_{2g} $$ d $$ d $$ 子壳部分占据所产生的轨道有序性(OO),以及 B 位点之间耦合产生的多种可能模式,在量子力学水平(全电子 $$ \mathrm{electron}\mathrm{electron} )上进行了研究、的量子力学水平(全电子 $\mathrm{all}\ \mathrm{electron} $$ 高斯型基集,B3LYP 混合函数)进行了研究。众多模式被分为 162 类等效构型。对于每种氟磷酸盐,每个类别都计算了一个代表。这四种化合物的表现相似:能量和体积(或晶胞参数)对 OO 模式的依赖性相同;跨能量区间较小(每个公式单位 1 至 2 mE h $$ {}_h $$),表明大多数构型在室温甚至低温下都被占据。考虑到相邻位点的相对轨道顺序的线性模型再现了每种化合物全集的能量顺序,这表明它可用于研究较大超级电池中的 OO。
t
2
g
d
orbital ordering patterns in KBF
3
(B = Sc, Ti, Fe, Co) perovskites
The orbital ordering (OO) resulting from the partial occupancy of the subshell of the transition metals in KBF (B = Sc, Ti, Ffe, Co) perovskites, and the many possible patterns arising from the coupling between the B sites, have been investigated at the quantum mechanical level ( Gaussian type basis set, B3LYP hybrid functional) in a 40 atoms supercell. The numerous patterns are distributed into 162 classes of equivalent configurations. For each fluoroperovskite, one representative per class has been calculated. The four compounds behave similarly: an identical dependence of the energy and volume (or cell parameters) on the OO pattern; the spanned energy interval is small (1 to 2 mE per formula unit), suggesting that most of the configurations are occupied at room and even at low temperature. A linear model, taking into account the relative orbital order in contiguous sites, reproduces the energy order in the full set for each compound, suggesting that it could be used for studying OO in larger supercells.
期刊介绍:
This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.