High-Pressure Synthesis, Crystal Structure, and Unusual Valence State of Novel Perovskite Oxide CaCu3Rh4O12
A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA′3B4O12-type perovskite structure. Synchrotron...
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| Veröffentlicht in: | Inorganic chemistry 2014-07, Vol.53 (14), p.7089-7091 |
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| container_title | Inorganic chemistry |
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| creator | Yamada, Ikuya Ochi, Mikiko Mizumaki, Masaichiro Hariki, Atsushi Uozumi, Takayuki Takahashi, Ryoji Irifune, Tetsuo |
| description | A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA′3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca2+Cu∼2.8+ 3Rh∼3.4+ 4O12, as opposed to the conventional Ca2+Cu2+ 3Rh4+ 4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial. |
| doi_str_mv | 10.1021/ic501341x |
| format | Article |
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Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA′3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca2+Cu∼2.8+ 3Rh∼3.4+ 4O12, as opposed to the conventional Ca2+Cu2+ 3Rh4+ 4O12. 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Chem</addtitle><description>A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA′3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca2+Cu∼2.8+ 3Rh∼3.4+ 4O12, as opposed to the conventional Ca2+Cu2+ 3Rh4+ 4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.</description><subject>Calcium Compounds - chemical synthesis</subject><subject>Calcium Compounds - chemistry</subject><subject>Hot Temperature</subject><subject>Oxides - chemical synthesis</subject><subject>Oxides - chemistry</subject><subject>Powder Diffraction</subject><subject>Pressure</subject><subject>Titanium - chemistry</subject><subject>X-Ray Absorption Spectroscopy</subject><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNo9kEtPwzAQhC0EglI48AeQL0gcGtiN7aQ9ooiXVFFEAXGLHGdLQ9Ok2HHV_nuMeJx2NPvtajSMnSBcIMR4WRkFKCRudlgPVQyRQnjbZT2AoDFJRgfs0LkPABgJmeyzg1gFjSrpscVd9T6PHi055y3x6bbp5uQqN-CZ3bpO13zaWW-6sBxw3ZT8pfHOB_tV19SYcNHpjng74w_tmmr-SLZdu0UVvMmmKolnOvPiaS4nGB-xvZmuHR3_zj6b3lw_Z3fReHJ7n12NIy0g7aISgHRaGjmikoQZCihA6yItMJa6wHKoCFQRD7UxmBKQlIWkWCa6GM1UKvrs_OfryrafnlyXLytnqK51Q613OSqZKhEjQkBPf1FfLKnMV7ZaarvN_-oJwNkPoI3LP1pvm5A7R8i_a8__axdfSghyQQ</recordid><startdate>20140721</startdate><enddate>20140721</enddate><creator>Yamada, Ikuya</creator><creator>Ochi, Mikiko</creator><creator>Mizumaki, Masaichiro</creator><creator>Hariki, Atsushi</creator><creator>Uozumi, Takayuki</creator><creator>Takahashi, Ryoji</creator><creator>Irifune, Tetsuo</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20140721</creationdate><title>High-Pressure Synthesis, Crystal Structure, and Unusual Valence State of Novel Perovskite Oxide CaCu3Rh4O12</title><author>Yamada, Ikuya ; Ochi, Mikiko ; Mizumaki, Masaichiro ; Hariki, Atsushi ; Uozumi, Takayuki ; Takahashi, Ryoji ; Irifune, Tetsuo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a307t-d00ea7dc49ede3c830b0aab7b124ab1d85e05b28acc17e0e44b4e246ab9f573</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Calcium Compounds - chemical synthesis</topic><topic>Calcium Compounds - chemistry</topic><topic>Hot Temperature</topic><topic>Oxides - chemical synthesis</topic><topic>Oxides - chemistry</topic><topic>Powder Diffraction</topic><topic>Pressure</topic><topic>Titanium - chemistry</topic><topic>X-Ray Absorption Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yamada, Ikuya</creatorcontrib><creatorcontrib>Ochi, Mikiko</creatorcontrib><creatorcontrib>Mizumaki, Masaichiro</creatorcontrib><creatorcontrib>Hariki, Atsushi</creatorcontrib><creatorcontrib>Uozumi, Takayuki</creatorcontrib><creatorcontrib>Takahashi, Ryoji</creatorcontrib><creatorcontrib>Irifune, Tetsuo</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Yamada, Ikuya</au><au>Ochi, Mikiko</au><au>Mizumaki, Masaichiro</au><au>Hariki, Atsushi</au><au>Uozumi, Takayuki</au><au>Takahashi, Ryoji</au><au>Irifune, Tetsuo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>High-Pressure Synthesis, Crystal Structure, and Unusual Valence State of Novel Perovskite Oxide CaCu3Rh4O12</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2014-07-21</date><risdate>2014</risdate><volume>53</volume><issue>14</issue><spage>7089</spage><epage>7091</epage><pages>7089-7091</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA′3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca2+Cu∼2.8+ 3Rh∼3.4+ 4O12, as opposed to the conventional Ca2+Cu2+ 3Rh4+ 4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>25000156</pmid><doi>10.1021/ic501341x</doi><tpages>3</tpages></addata></record> |
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| subjects | Calcium Compounds - chemical synthesis Calcium Compounds - chemistry Hot Temperature Oxides - chemical synthesis Oxides - chemistry Powder Diffraction Pressure Titanium - chemistry X-Ray Absorption Spectroscopy |
| title | High-Pressure Synthesis, Crystal Structure, and Unusual Valence State of Novel Perovskite Oxide CaCu3Rh4O12 |
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