{"title":"电子俘获负离子质谱法中多氯二苯并呋喃和二苯并二恶英分子自由基阴离子丰度与计算的最低未占据分子轨道能的关系:负亚稳离子存在的证据。","authors":"J A Laramée, Y S Chang, B C Arbogast, M L Deinzer","doi":"10.1002/bms.1200170112","DOIUrl":null,"url":null,"abstract":"<p><p>Relationships were found between experimentally measured molecular radical anion abundances and calculated lowest unoccupied molecular orbital energies (epsilon LUMO) for polychlorodibenzofurans and polychlorodibenzo-p-dioxins. Anion abundances were measured using standard mass spectrometric techniques, while epsilon LUMO were calculated by the 'Complete Neglect of Differential Overlap' method. Polychlorodibenzofurans with calculated epsilon LUMO greater than or equal to 1.6 eV show 0% molecular radical anion and those with epsilon LUMO less than or equal to 1.4 eV show greater than or equal to 80% molecular radical anion abundance. Similarly, the molecular radical anion is absent for polychlorodibenzo-p-dioxins with calculated epsilon LUMO greater than or equal to 2.0 eV. A trend towards greater molecular radical ion relative abundance appears for 2.0 eV greater than or equal to epsilon LUMO greater than or equal to 1.0 eV and a maximum is reached around 1 eV, whereupon the molecular ion abundance diminishes with lower epsilon LUMO. B/E linked scan analysis indicates that chlorodioxins with epsilon LUMO less than 1 eV give increasing amounts of metastable anions.</p>","PeriodicalId":8924,"journal":{"name":"Biomedical & environmental mass spectrometry","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"1988-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1002/bms.1200170112","citationCount":"16","resultStr":"{\"title\":\"Relationship of molecular radical anion abundance and calculated lowest unoccupied molecular orbital energies for polychlorinated dibenzofurans and dibenzodioxins in electron capture negative ion mass spectrometry: evidence for negative metastable ions.\",\"authors\":\"J A Laramée, Y S Chang, B C Arbogast, M L Deinzer\",\"doi\":\"10.1002/bms.1200170112\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Relationships were found between experimentally measured molecular radical anion abundances and calculated lowest unoccupied molecular orbital energies (epsilon LUMO) for polychlorodibenzofurans and polychlorodibenzo-p-dioxins. Anion abundances were measured using standard mass spectrometric techniques, while epsilon LUMO were calculated by the 'Complete Neglect of Differential Overlap' method. Polychlorodibenzofurans with calculated epsilon LUMO greater than or equal to 1.6 eV show 0% molecular radical anion and those with epsilon LUMO less than or equal to 1.4 eV show greater than or equal to 80% molecular radical anion abundance. Similarly, the molecular radical anion is absent for polychlorodibenzo-p-dioxins with calculated epsilon LUMO greater than or equal to 2.0 eV. A trend towards greater molecular radical ion relative abundance appears for 2.0 eV greater than or equal to epsilon LUMO greater than or equal to 1.0 eV and a maximum is reached around 1 eV, whereupon the molecular ion abundance diminishes with lower epsilon LUMO. B/E linked scan analysis indicates that chlorodioxins with epsilon LUMO less than 1 eV give increasing amounts of metastable anions.</p>\",\"PeriodicalId\":8924,\"journal\":{\"name\":\"Biomedical & environmental mass spectrometry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1988-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1002/bms.1200170112\",\"citationCount\":\"16\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Biomedical & environmental mass spectrometry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1002/bms.1200170112\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Biomedical & environmental mass spectrometry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/bms.1200170112","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Relationship of molecular radical anion abundance and calculated lowest unoccupied molecular orbital energies for polychlorinated dibenzofurans and dibenzodioxins in electron capture negative ion mass spectrometry: evidence for negative metastable ions.
Relationships were found between experimentally measured molecular radical anion abundances and calculated lowest unoccupied molecular orbital energies (epsilon LUMO) for polychlorodibenzofurans and polychlorodibenzo-p-dioxins. Anion abundances were measured using standard mass spectrometric techniques, while epsilon LUMO were calculated by the 'Complete Neglect of Differential Overlap' method. Polychlorodibenzofurans with calculated epsilon LUMO greater than or equal to 1.6 eV show 0% molecular radical anion and those with epsilon LUMO less than or equal to 1.4 eV show greater than or equal to 80% molecular radical anion abundance. Similarly, the molecular radical anion is absent for polychlorodibenzo-p-dioxins with calculated epsilon LUMO greater than or equal to 2.0 eV. A trend towards greater molecular radical ion relative abundance appears for 2.0 eV greater than or equal to epsilon LUMO greater than or equal to 1.0 eV and a maximum is reached around 1 eV, whereupon the molecular ion abundance diminishes with lower epsilon LUMO. B/E linked scan analysis indicates that chlorodioxins with epsilon LUMO less than 1 eV give increasing amounts of metastable anions.