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Chiroptical Inversion for Isolated Vibronic Transitions of Supersonic Beam-Cooled Molecules

Abstract

Circular dichroism - resonance-enhanced multiphoton ionization (CD-REMPI) was used for CD measurements on several single vibronic transitions of supersonic beam-cooled (R)-(+)-1-phenylethanol. Due to the low molecular densities within a supersonic beam and the expected small anisotropy factor of 1-phenylethanol in the permille region, the precision of the experimental method had to be significantly improved. Therefore, a single laser pulse evaluation combined with a twin-peak technique enabled within the used supersonic beam setup is presented. For the electronic transition S_0→S_1 of (R)-(+)-1-phenylethanol (π→π^* transition of the phenyl ring at 266 nm) ten different vibrational modes as well as the 0_0^0-transition were investigated with one-color (1+1) CD-REMPI. The results deliver new experimental insights on the influence of molecular vibrations on the anisotropy factor. TD-DFT theoretical predictions show how the angle between the electronic and magnetic transition dipole moments of the electronic transition can be modified by different vibrational modes, making even a flip of the sign of the anisotropy factor possible.

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Publication details

The article was received on 20 Apr 2017, accepted on 19 Jun 2017 and first published on 19 Jun 2017


Article type: Paper
DOI: 10.1039/C7CP02596C
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Chiroptical Inversion for Isolated Vibronic Transitions of Supersonic Beam-Cooled Molecules

    J. H. T. Lepelmeier, J. L. Alonso-Gómez, F. Mortaheb, U. Boesl, U. Heiz and A. Kartouzian, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP02596C

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