High-resolution cavity ringdown spectroscopy of the jet-cooled propyl peroxy radical C3H7O2

Literature Information

Publication Date 2010-03-18
DOI 10.1039/B924323B
Impact Factor 3.676
Authors

Gabriel M. P. Just, Patrick Rupper, Terry A. Miller, W. Leo Meerts


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Abstract

We have obtained high resolution, partially rotationally resolved, jet-cooled cavity ringdown spectra of the origin band of the à ← electronic transition of two of the five conformers (G1G2 and G1T2) of the normal propyl peroxy radical, C3H7O2, as well as the G conformer of the iso-propyl peroxy radical isomer. This transition, located in the near infrared, was studied using a narrow band laser source (≲250 MHz) and a supersonic slit-jet expansion coupled with an electric discharge allowing us to obtain rotational temperatures of about 15 K. All three spectra have been successfully fitted using an evolutionary algorithm approach with a Hamiltonian including rotational and spin-rotational terms. Excellent agreement with the experimental spectra was obtained by fitting seven molecular parameters in each of the ground and the first excited electronic states as well as the band origin of the electronic transition. These parameters are compared with the results from electronic structure calculations. This analysis confirms unambiguously the previous room-temperature conformer assignments that were based upon quantum chemistry calculations.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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