{"title":"从石英(qtz)到钻石(dia)碳拓扑:从晶体化学和 DFT 研究逐步推进的原理","authors":"Samir F. Matar","doi":"10.1016/j.progsolidstchem.2024.100453","DOIUrl":null,"url":null,"abstract":"<div><p><em>From crystal chemistry and density functional theory DFT calculations, a stepwise rationale is proposed for the transformation from standalone distorted tetrahedron α-</em>C<sub>5</sub> <em>favored over standalone regular tetrahedron β-C</em><sub><em>5</em></sub> <em>to high density – ultra hard orthorhombic α-C</em><sub><em>6</em></sub> <em>and β-C</em><sub><em>6</em></sub> <em>with</em> <strong><em>qtz</em></strong> <em>(quartz-based) topology characterized by 3D arrangements of distorted tetrahedra to lower density</em> <strong><em>dia</em></strong><em>-C topology (diamond-like, with regular</em> C4 <em>tetrahedra). Progressive C insertions into orthorhombic α-</em>C<sub>5</sub><em>, α-C</em><sub><em>6</em></sub><em>, and lastly into C</em><sub><em>7</em></sub> <em>were operated leading to ultimate C</em><sub><em>8</em></sub> <em>stoichiometry identified as diamond-like. C</em><sub><em>7</em></sub> <em>was also used as template to devise C</em><sub><em>3</em></sub><em>N</em><sub><em>4</em></sub> <em>carbonitride with exceptional mechanical properties. The induced structural and physical changes are</em> supported <em>with elastic properties pointing to ultra-hardness, larger for</em> <strong><em>qtz</em></strong> <em>α,β-C</em><sub><em>6</em></sub> <em>than</em> <strong><em>dia</em></strong> <em>C</em><sub><em>8</em></sub> <em>and inferred dynamic stability for all stoichiometries from the phonons band structures. The thermodynamic quantities as the specific heat were compared with diamond experimental C</em><sub><em>V</em></sub><em>. The electronic band structures reveal semi-conducting C</em><sub><em>6</em></sub><em>, metallic C</em><sub><em>7</em></sub> <em>characterized by diamond-defect structure, and insulating C</em><sub><em>8</em></sub><em>. The results are meant to help further systemic understanding of tetrahedral carbon allotropes.</em></p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":9.1000,"publicationDate":"2024-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"From quartz (qtz) to diamond (dia) carbon topologies: Stepwise rationale from crystal chemistry and DFT investigations\",\"authors\":\"Samir F. Matar\",\"doi\":\"10.1016/j.progsolidstchem.2024.100453\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><em>From crystal chemistry and density functional theory DFT calculations, a stepwise rationale is proposed for the transformation from standalone distorted tetrahedron α-</em>C<sub>5</sub> <em>favored over standalone regular tetrahedron β-C</em><sub><em>5</em></sub> <em>to high density – ultra hard orthorhombic α-C</em><sub><em>6</em></sub> <em>and β-C</em><sub><em>6</em></sub> <em>with</em> <strong><em>qtz</em></strong> <em>(quartz-based) topology characterized by 3D arrangements of distorted tetrahedra to lower density</em> <strong><em>dia</em></strong><em>-C topology (diamond-like, with regular</em> C4 <em>tetrahedra). Progressive C insertions into orthorhombic α-</em>C<sub>5</sub><em>, α-C</em><sub><em>6</em></sub><em>, and lastly into C</em><sub><em>7</em></sub> <em>were operated leading to ultimate C</em><sub><em>8</em></sub> <em>stoichiometry identified as diamond-like. C</em><sub><em>7</em></sub> <em>was also used as template to devise C</em><sub><em>3</em></sub><em>N</em><sub><em>4</em></sub> <em>carbonitride with exceptional mechanical properties. The induced structural and physical changes are</em> supported <em>with elastic properties pointing to ultra-hardness, larger for</em> <strong><em>qtz</em></strong> <em>α,β-C</em><sub><em>6</em></sub> <em>than</em> <strong><em>dia</em></strong> <em>C</em><sub><em>8</em></sub> <em>and inferred dynamic stability for all stoichiometries from the phonons band structures. The thermodynamic quantities as the specific heat were compared with diamond experimental C</em><sub><em>V</em></sub><em>. The electronic band structures reveal semi-conducting C</em><sub><em>6</em></sub><em>, metallic C</em><sub><em>7</em></sub> <em>characterized by diamond-defect structure, and insulating C</em><sub><em>8</em></sub><em>. The results are meant to help further systemic understanding of tetrahedral carbon allotropes.</em></p></div>\",\"PeriodicalId\":415,\"journal\":{\"name\":\"Progress in Solid State Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.1000,\"publicationDate\":\"2024-06-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Progress in Solid State Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0079678624000165\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Progress in Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0079678624000165","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
From quartz (qtz) to diamond (dia) carbon topologies: Stepwise rationale from crystal chemistry and DFT investigations
From crystal chemistry and density functional theory DFT calculations, a stepwise rationale is proposed for the transformation from standalone distorted tetrahedron α-C5favored over standalone regular tetrahedron β-C5to high density – ultra hard orthorhombic α-C6and β-C6withqtz(quartz-based) topology characterized by 3D arrangements of distorted tetrahedra to lower densitydia-C topology (diamond-like, with regular C4 tetrahedra). Progressive C insertions into orthorhombic α-C5, α-C6, and lastly into C7were operated leading to ultimate C8stoichiometry identified as diamond-like. C7was also used as template to devise C3N4carbonitride with exceptional mechanical properties. The induced structural and physical changes are supported with elastic properties pointing to ultra-hardness, larger forqtzα,β-C6thandiaC8and inferred dynamic stability for all stoichiometries from the phonons band structures. The thermodynamic quantities as the specific heat were compared with diamond experimental CV. The electronic band structures reveal semi-conducting C6, metallic C7characterized by diamond-defect structure, and insulating C8. The results are meant to help further systemic understanding of tetrahedral carbon allotropes.
期刊介绍:
Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.