Mass-Selected Circular Dichroism of Supersonic-Beam-Cooled [D4]-(R)-(+)-3-Methylcyclopentanone

Jörn Lepelmeier, Katharina Titze, Aras Kartouzian, Ulrich Boesl, Ulrich Heiz

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

UV spectroscopy and electronic circular dichroism (ECD) experiments on supersonic-beam-cooled deuterated (R)-(+)-3-methylcyclopentanone ([D4]-(R)-(+)-3-MCP) have been performed by using a laser mass spectrometer. The spectral resolution not only allowed excitation and CD measurements for single vibronic transitions but also for the rotational P, Q, and R branches of these transitions. The investigated n →π(1804 2501) transition showed the largest anisotropy factor ever observed for chiral molecules in the gas phase, which, due to residual saturation of the excited transition, represents only a lower limit for the real anisotropy factor. Furthermore, one-color (1+1+1) and two-color (1+1′) resonance-enhanced multiphoton ionization (REMPI) measurements were performed and the effusive-beam (room temperature) and supersonic-beam results for [D4]-(R)-(+)-3-MCP were compared. These results allowed a differentiation between single-step ECD (comparable to conventional ECD) and cumulative ECD (only possible in multiphoton excitation) under supersonic-beam conditions.

Original languageEnglish
Pages (from-to)4052-4058
Number of pages7
JournalChemPhysChem
Volume17
Issue number24
DOIs
StatePublished - 15 Dec 2016

Keywords

  • circular dichroism
  • mass spectrometry
  • resonance-enhanced multiphoton ionization
  • rotational spectroscopy
  • supersonic beam cooling

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