Vibrationally resolved circular dichroism spectra of a molecule with isotopically engendered chirality.
We present a theoretical study of vibrationally resolved circular dichroism spectra, both in the adiabatic and non-adiabatic frameworks, with a full account of Franck-Condon and Herzberg-Teller vibrational contributions for the former. Model calculations have been performed on 2(R)-deuteriocyclopentanone, whose chirality is due solely to isotopic substitution. This molecule has two distinct, nearly isoenergetic, half-chair conformations in equilibrium, and its demanding nature in terms of computational accuracy makes it a perfect candidate for performing a detailed comparison between different vibronic models. Comparisons are made with experimental spectra, and we also consider temperature effects. In order to reproduce the experimental spectrum, it is necessary to consider the geometry relaxation occurring during the n→π* transition.
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Na
N
Lin
Harald
H
Solheim
Kenneth
K
Ruud
Marcel
M
Nooijen
Fabrizio
F
Santoro
Xian
X
Zhao
Marcin
M
Kwit
Pawel
P
Skowronek
D002942:Circular Dichroism; D003517:Cyclopentanes / Q000737:chemistry*; D007553:Isotope Labeling; D011789:Quantum Theory; D014732:Vibration
D003517:Cyclopentanes; C007201:cyclopentanone