{"title":"WH6和WF6的密度泛函计算","authors":"Noppawan Tanpipat, Jon Baker","doi":"10.1021/jp961633w","DOIUrl":null,"url":null,"abstract":"<p >We present the results of a computational study on both WH<sub>6</sub> and WF<sub>6</sub> using a relativistic pseudopotential on tungsten, comparing results at the HF and MP2 levels with density functional calculations using local (SVWN), nonlocal (BLYP), and hybrid HF-DFT (ACM) functionals. In agreement with the earlier all-electron HF study of Schaefer and co-workers (<i>J</i>. <i>Chem</i>. <i>Phys</i>. <b>1993</b>, <i>98</i>, 508), we find that the ground state geometry of WH<sub>6</sub> is far from octahedral; instead, there are four low-lying structures of <i>C</i><sub>3<i>v</i></sub> (2) and <i>C</i><sub>5<i>v</i></sub> (2) symmetry. Barrier heights for interconversion of these isomers are low, indicating a highly fluxional molecule. In contrast, the octahedral structure appears to be the only stable species on the ground state potential energy surface of WF<sub>6</sub>. It derives its stability from the greater ionic character of the W?F bond compared to that of W?H. </p>","PeriodicalId":58,"journal":{"name":"The Journal of Physical Chemistry ","volume":null,"pages":null},"PeriodicalIF":2.7810,"publicationDate":"1996-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1021/jp961633w","citationCount":"23","resultStr":"{\"title\":\"Density Functional Calculations on WH6 and WF6\",\"authors\":\"Noppawan Tanpipat, Jon Baker\",\"doi\":\"10.1021/jp961633w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We present the results of a computational study on both WH<sub>6</sub> and WF<sub>6</sub> using a relativistic pseudopotential on tungsten, comparing results at the HF and MP2 levels with density functional calculations using local (SVWN), nonlocal (BLYP), and hybrid HF-DFT (ACM) functionals. In agreement with the earlier all-electron HF study of Schaefer and co-workers (<i>J</i>. <i>Chem</i>. <i>Phys</i>. <b>1993</b>, <i>98</i>, 508), we find that the ground state geometry of WH<sub>6</sub> is far from octahedral; instead, there are four low-lying structures of <i>C</i><sub>3<i>v</i></sub> (2) and <i>C</i><sub>5<i>v</i></sub> (2) symmetry. Barrier heights for interconversion of these isomers are low, indicating a highly fluxional molecule. In contrast, the octahedral structure appears to be the only stable species on the ground state potential energy surface of WF<sub>6</sub>. It derives its stability from the greater ionic character of the W?F bond compared to that of W?H. </p>\",\"PeriodicalId\":58,\"journal\":{\"name\":\"The Journal of Physical Chemistry \",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7810,\"publicationDate\":\"1996-12-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1021/jp961633w\",\"citationCount\":\"23\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry \",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jp961633w\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry ","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jp961633w","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
We present the results of a computational study on both WH6 and WF6 using a relativistic pseudopotential on tungsten, comparing results at the HF and MP2 levels with density functional calculations using local (SVWN), nonlocal (BLYP), and hybrid HF-DFT (ACM) functionals. In agreement with the earlier all-electron HF study of Schaefer and co-workers (J. Chem. Phys. 1993, 98, 508), we find that the ground state geometry of WH6 is far from octahedral; instead, there are four low-lying structures of C3v (2) and C5v (2) symmetry. Barrier heights for interconversion of these isomers are low, indicating a highly fluxional molecule. In contrast, the octahedral structure appears to be the only stable species on the ground state potential energy surface of WF6. It derives its stability from the greater ionic character of the W?F bond compared to that of W?H.