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Diamagnetic Raman Optical Activity of Chlorine, Bromine, and Iodine Gases
Author(s) -
Šebestík Jaroslav,
Kapitán Josef,
Pačes Ondřej,
Bouř Petr
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201600058
Subject(s) - diamagnetism , excited state , chemistry , raman spectroscopy , raman scattering , paramagnetism , raman optical activity , zeeman effect , bromine , molecule , atomic physics , molecular physics , nuclear magnetic resonance , chemical physics , condensed matter physics , magnetic field , physics , optics , organic chemistry , quantum mechanics
Magnetic Raman optical activity of gases provides unique information about their electric and magnetic properties. Magnetic Raman optical activity has recently been observed in a paramagnetic gas ( Angew. Chem. Int. Ed . 2012 , 51 , 11058; Angew. Chem . 2012 , 124 , 11220). In diamagnetic molecules, it has been considered too weak to be measurable. However, in chlorine, bromine and iodine vapors, we could detect a significant signal as well. Zeeman splitting of electronic ground‐state energy levels cannot rationalize the observed circular intensity difference (CID) values of about 10 −4 . These are explicable by participation of paramagnetic excited electronic states. Then a simple model including one electronic excited state provides reasonable spectral intensities. The results suggest that this kind of scattering by diamagnetic molecules is a general event observable under resonance conditions. The phenomenon sheds new light on the role of excited states in the Raman scattering, and may be used to probe molecular geometry and electronic structure.