Research & Teaching Faculty

Default Header Image

Accurate density-functional calculation of core-electron binding energies of some substituted benzenes

TitleAccurate density-functional calculation of core-electron binding energies of some substituted benzenes
Publication TypeJournal Article
Year of Publication2000
AuthorsTakahata, Y, Chong, DP
JournalBulletin of the Chemical Society of Japan
Volume73
Pagination2453-2460
Date PublishedNov
Type of ArticleArticle
ISBN Number0009-2673
KeywordsAPPROXIMATION, BORON, DERIVATIVES, GAS, PARAMETERS, RAY PHOTOELECTRON-SPECTROSCOPY, SPECTRA, ZETA BASIS-SET
Abstract

The core electron binding energies (CEBE’s) of benzene, seven monosubstituted benzenes (Ph-X) and one disubstituted benzene (p-NH2-C6H4-NO2) were calculated using density-functional theory (DFT). The unrestricted generalized transition-state (uGTS) model was employed. The DeMon DFT program with a combined functional of Becke’s exchange (B88) with Perdew’s correlation (P86) was used. The average absolute deviation of the calculated CEBE’s of the title compounds was 0.3 eV when the cc-pVDZ basis set was used. The "CEBE shift" of the ring carbon in Ph-X was calculated while taking the CEBE on the ring carbon in Ph-H as a reference. The thus-calculated CEBE shifts agree with experiment within the value of the average absolute deviation, 0.1 eV. The signs and quantitative numerical values of the CEBE shifts are very close to the corresponding Hammett sigma constants.

URL<Go to ISI>://000165701500004