Xiang Tiancheng, Zhao Yanru, Xu Jingli, Hu Chaopeng
{"title":"2NCO + 2N2H反应的理论研究","authors":"Xiang Tiancheng, Zhao Yanru, Xu Jingli, Hu Chaopeng","doi":"10.1016/j.theochem.2010.07.019","DOIUrl":null,"url":null,"abstract":"<div><p>The singlet and triplet potential surfaces of the <sup>2</sup>NCO<!--> <!-->+<!--> <sup>2</sup>N<sub>2</sub>H reaction have been investigated at the B3LYP/6-311G (d,p) level. The single-point energy calculations are performed at the high-level CCSD (T)/6-311G (d,p) for more accurate energy values. DFT calculations reveal the reaction mechanism to be mainly a barrierless addition of <sup>2</sup>NCO to <sup>2</sup>N<sub>2</sub>H leading to an intermediate <sup>1</sup>im3 (OCN–N<sub>2</sub>H) on the singlet potential surface. The adduct <sup>1</sup>im3 goes through an H shift from N<sub>2</sub>H to NCO, forming the product of HNCO and N<sub>2</sub>. Due to the higher barrier of initial association, the reaction is more difficult on the triplet potential surface.</p></div>","PeriodicalId":16419,"journal":{"name":"Journal of Molecular Structure-theochem","volume":"958 1","pages":"Pages 10-14"},"PeriodicalIF":0.0000,"publicationDate":"2010-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.theochem.2010.07.019","citationCount":"3","resultStr":"{\"title\":\"A theoretical study of the 2NCO + 2N2H reaction\",\"authors\":\"Xiang Tiancheng, Zhao Yanru, Xu Jingli, Hu Chaopeng\",\"doi\":\"10.1016/j.theochem.2010.07.019\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The singlet and triplet potential surfaces of the <sup>2</sup>NCO<!--> <!-->+<!--> <sup>2</sup>N<sub>2</sub>H reaction have been investigated at the B3LYP/6-311G (d,p) level. The single-point energy calculations are performed at the high-level CCSD (T)/6-311G (d,p) for more accurate energy values. DFT calculations reveal the reaction mechanism to be mainly a barrierless addition of <sup>2</sup>NCO to <sup>2</sup>N<sub>2</sub>H leading to an intermediate <sup>1</sup>im3 (OCN–N<sub>2</sub>H) on the singlet potential surface. The adduct <sup>1</sup>im3 goes through an H shift from N<sub>2</sub>H to NCO, forming the product of HNCO and N<sub>2</sub>. Due to the higher barrier of initial association, the reaction is more difficult on the triplet potential surface.</p></div>\",\"PeriodicalId\":16419,\"journal\":{\"name\":\"Journal of Molecular Structure-theochem\",\"volume\":\"958 1\",\"pages\":\"Pages 10-14\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2010-10-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/j.theochem.2010.07.019\",\"citationCount\":\"3\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Structure-theochem\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0166128010004604\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Structure-theochem","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0166128010004604","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
The singlet and triplet potential surfaces of the 2NCO + 2N2H reaction have been investigated at the B3LYP/6-311G (d,p) level. The single-point energy calculations are performed at the high-level CCSD (T)/6-311G (d,p) for more accurate energy values. DFT calculations reveal the reaction mechanism to be mainly a barrierless addition of 2NCO to 2N2H leading to an intermediate 1im3 (OCN–N2H) on the singlet potential surface. The adduct 1im3 goes through an H shift from N2H to NCO, forming the product of HNCO and N2. Due to the higher barrier of initial association, the reaction is more difficult on the triplet potential surface.
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