Conformational analysis of the isomers of lewisite

✍ Scribed by Joseph J. Urban; Robert L. von Tersch

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 61 KB
• Volume: 12
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199902)12:2<95::aid-poc91>3.0.co;2-v

✦ Synopsis

Chlorovinyldichloroarsine, also known as lewisite, is a powerful vesicant that has been used in the past as a chemical weapon. Its extreme toxicity makes obtaining experimental data to characterize this notorious chemical system very challenging. In this work, ab initio calculations were carried out on the geminal, cis and trans isomers of lewisite at a variety of levels of theory employing both all-electron and effective-core potential basis sets. The aims were to ascertain the relative stability of these three isomeric forms of lewisite and to characterize their structures, dipole moments and conformational preferences. The trans isomer of lewisite was found to be the most stable and the geminal isomer the least stable. This is consistent with the experimental data available on the compositions of lewisite mixtures.