New light on acetone: a master equation model for gas phase photophysics and photochemistry

Abstract

This paper presents a unified model of gas phase acetone photophysics and photochemistry that is based on experimental data, which are reviewed and discussed in detail, and a detailed microcanonical master equation formulation. The model accounts for experimental measurements in molecular beams as well as in thermal systems, leads to a new interpretation of some experiments, and reveals a fundamental property of quantum yield measurements that are relevant to atmospheric chemistry. It also furnishes a platform for future theoretical and experimental developments.

GRAPHICAL ABSTRACT

KEYWORDS:

• Fluorescence
• internal conversion
• intersystem crossing
• quantum yield
• master equation

Acknowledgements

Thanks go to A. R. Ravishankara for urging me to jump into this acetone bath! Thanks also go to Keiran N. Rowell, Meredith J. T. Jordan, and Scott H. Kable for helpful comments on an early draft of the manuscript and for generously providing vibrational frequencies and other parameters from their recent calculations [37]. Great appreciation also goes to the faculty and staff in my department here at the University of Michigan. This paper is dedicated to Jürgen Troe on the occasion of his 80th birthday and to John Stanton on his 60th birthday. Jürgen Troe has made seminal contributions to both experimental and theoretical chemical kinetics. John Stanton has developed ab initio quantum chemistry methods that are driving progress in thermochemistry, spectroscopy, and chemical kinetics.

Disclosure statement

No potential conflict of interest was reported by the author(s).