Kinetics and Photochemistry Laboratory

JKPL Lab
Left: A high-temperature (300 – 700 K) laser photolysis/laser-induced fluorescence apparatus for studies of radical species important for exoplanet atmospheres.
Right: Laser photolysis/broadband UV-vis absorption spectroscopy apparatus for the measurements of rate constants of radical reactions (e.g. Criegee intermediates, ClCO) of importance in Earth’s and Venus’ atmosphere.

The JPL Kinetics and Photochemistry Laboratory (JKPL) studies elementary chemical reactions in the atmospheres of Earth and planetary systems. Most of these reactions involve highly reactive free radicals important in the odd oxygen, hydrogen, nitrogen, halogen and sulfur families. These radicals, including those formed from the decomposition of industrial chemicals such as chlorofluorocarbons (CFCs), catalyze the destruction of stratospheric ozone, and cause the well-known Antarctic Ozone Hole. They are also important in the formation of excess ozone and other harmful air pollutants in the lower atmosphere, and produce photochemical smog in cities and downwind areas.

In JKPL, we use state-of-the-art techniques to measure rate coefficients of elementary gas-phase reactions, and quantum yields of photochemical processes under conditions of pressure and temperature relevant to atmospheric modeling. Lasers of many types are used to initiate chemical reactions and probe the reaction kinetics in real time using fluorescence, cavity ringdown, and long-path and cavity-enhanced absorption. Other analysis methods include Chemical Ionization Mass Spectroscopy, high resolution Fourier Transform Infrared (FTIR) spectroscopy and matrix isolation spectroscopy. The laboratory also measures UV-visible-IR absorption cross sections and spectroscopic line parameters of atmospheric molecules.

The overall objective of JKPL is to provide laboratory data that will support models that assess issues such as stratospheric ozone depletion and the coupling between air quality and climate change. JKPL coordinates the activities of the NASA Panel for Data Evaluation, a group of specialists in laboratory kinetics and photochemistry who publish a periodic critical evaluation of data for use in atmospheric models and other studies. These evaluations includes recommended rate coefficients, equilibrium constants, photochemical parameters, aerosol chemistry parameters and thermodynamic data for modeling the atmospheres of Earth and planets. The evaluation is available for download on the Panel’s web site.

In addition, the JPKL studies the atmospheric chemistry of the planets within our solar system and extrasolar planets which is also driven by highly reactive radical species. The JKPL group is leading research into Venus’ upper atmosphere, investigating chemical kinetics and reactive intermediate spectroscopy central to: (1) how molecular oxygen is sequestered (despite a large hypothesized production rate), (2) catalyzed carbon dioxide production, (3) the photochemical production of sulfur dioxide at higher altitudes and (4) the “unknown absorber” in the UV and (5) polysulfur chemistry. Experimentally derived parameters are used in conjunction with photochemical models to assess the impact of our measurements on the Venus atmosphere.

Exoplanet observations from NASA mission such as JWST (James Webb Space Telescope) have revealed a bonanza of complex chemistry: photochemically-produced molecules, clouds and haze formation, etc. These atmospheric observations of exoplanets have in turn revealed knowledge gaps in the underlying chemistry of computational photochemical models.   JPKL are studying reactions the reactions of radical species important for exoplanet atmospheres (e.g., NH, NH2, PH2, OH, SH, CH3S) over large temperature and pressure range applicable to exoplanetary atmospheres.