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The prediction of the circular dichroism of the benzene chromophore: TDDFT calculations and sector rules
Author(s) -
Pescitelli Gennaro,
Di Bari Lorenzo,
Caporusso Anna Maria,
Salvadori Piero
Publication year - 2008
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.20460
Subject(s) - chromophore , time dependent density functional theory , chemistry , chirality (physics) , circular dichroism , benzene , density functional theory , spectral line , range (aeronautics) , series (stratigraphy) , computational chemistry , crystallography , stereochemistry , photochemistry , organic chemistry , quantum mechanics , physics , chiral symmetry , paleontology , materials science , nambu–jona lasinio model , composite material , biology , quark
The CD spectra of the series PhCH(Me)R, with R = Et ( 1 ), n Pr ( 2 ), i Pr ( 3 ), and t Bu ( 4 ), are reported ( 1 – 3 for the first time) at room temperature in the 185–280 nm range and at 183 K. These purely hydrocarbon compounds represent the simplest chiral systems containing the phenyl chromophore and exhibit Cotton effects exclusively allied with the benzene transitions. The bands in 1 L a and 1 L b regions were checked against the available sector rules, with discordant outcomes. Time‐dependent density‐functional theory calculations, with various functionals and basis sets tested, correctly reproduced the prominent CD bands observed for 1 – 4 . Chirality, 2008. © 2007 Wiley‐Liss, Inc.