D. Cagardová, M. Michalík, E. Klein, V. Lukeš, Z. Marković
{"title":"芳族化合物的电离势、质子亲和和键解离焓的DFT和从头计算","authors":"D. Cagardová, M. Michalík, E. Klein, V. Lukeš, Z. Marković","doi":"10.2478/acs-2019-0032","DOIUrl":null,"url":null,"abstract":"Abstract Theoretical study of phenol, thiophenol, benzeneselenol, aniline and their para-amino and paranitro derivatives is presented. Neutral molecules, their deprotonated forms, neutral radicals, and radical cations were studied using three Density Functional Theory (DFT) functionals as well as combined DFT and ab initio G4 method in order to calculate the N—H, O—H, S—H, and Se—H bond dissociation enthalpies (BDE), proton affinities of corresponding anions (PA) and ionization potentials (IP) of studied compounds. These quantities represent fundamental reaction enthalpies related to the radical scavenging action of primary antioxidants. Calculated values were compared with available experimental data to assess applicability of the computational approaches employed. M06-2X/6-311++G(d,p) and G4 methods showed the best agreement with the available experimental gas-phase reaction enthalpies.","PeriodicalId":7088,"journal":{"name":"Acta Chimica Slovaca","volume":"12 1","pages":"225 - 240"},"PeriodicalIF":0.9000,"publicationDate":"2019-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"3","resultStr":"{\"title\":\"DFT and ab initio calculations of ionization potentials, proton affinities and bond dissociation enthalpies of aromatic compounds\",\"authors\":\"D. Cagardová, M. Michalík, E. Klein, V. Lukeš, Z. Marković\",\"doi\":\"10.2478/acs-2019-0032\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Abstract Theoretical study of phenol, thiophenol, benzeneselenol, aniline and their para-amino and paranitro derivatives is presented. Neutral molecules, their deprotonated forms, neutral radicals, and radical cations were studied using three Density Functional Theory (DFT) functionals as well as combined DFT and ab initio G4 method in order to calculate the N—H, O—H, S—H, and Se—H bond dissociation enthalpies (BDE), proton affinities of corresponding anions (PA) and ionization potentials (IP) of studied compounds. These quantities represent fundamental reaction enthalpies related to the radical scavenging action of primary antioxidants. Calculated values were compared with available experimental data to assess applicability of the computational approaches employed. M06-2X/6-311++G(d,p) and G4 methods showed the best agreement with the available experimental gas-phase reaction enthalpies.\",\"PeriodicalId\":7088,\"journal\":{\"name\":\"Acta Chimica Slovaca\",\"volume\":\"12 1\",\"pages\":\"225 - 240\"},\"PeriodicalIF\":0.9000,\"publicationDate\":\"2019-10-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"3\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Chimica Slovaca\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.2478/acs-2019-0032\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Chimica Slovaca","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.2478/acs-2019-0032","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
DFT and ab initio calculations of ionization potentials, proton affinities and bond dissociation enthalpies of aromatic compounds
Abstract Theoretical study of phenol, thiophenol, benzeneselenol, aniline and their para-amino and paranitro derivatives is presented. Neutral molecules, their deprotonated forms, neutral radicals, and radical cations were studied using three Density Functional Theory (DFT) functionals as well as combined DFT and ab initio G4 method in order to calculate the N—H, O—H, S—H, and Se—H bond dissociation enthalpies (BDE), proton affinities of corresponding anions (PA) and ionization potentials (IP) of studied compounds. These quantities represent fundamental reaction enthalpies related to the radical scavenging action of primary antioxidants. Calculated values were compared with available experimental data to assess applicability of the computational approaches employed. M06-2X/6-311++G(d,p) and G4 methods showed the best agreement with the available experimental gas-phase reaction enthalpies.