Ultraviolet photochemistry of buta-1,3- and buta-1,2-dienes: laser spectroscopic absolute hydrogen atom quantum yield and translational energy distribution measurements

The Journal of Chemical Physics
A HanfRajesh K Vatsa

Abstract

Using pulsed H-atom Lyman-alpha laser-induced fluorescence spectroscopy along with a photolytic calibration approach, absolute H-atom product quantum yields of phi(H-b13d) = (0.32+/-0.04) and phi(H-b12d) = (0.36+/-0.04) were measured under collision-free conditions for the 193 nm gas-phase laser flash photolysis of buta-1,3- and buta-1,2-diene at room temperature, which demonstrate that nascent H-atom formation is of comparable importance for both parent molecules. Comparison of the available energy fraction, f(T-b13d) = (0.22+/-0.03) and f(T-b12d) = (0.13+/-0.01), released as H+C(4)H(5) product translational energy with results of impulsive and statistical energy partitioning modeling calculations indicates that for both, buta-1,3- and buta-1,2-diene, H-atom formation is preceded by internal conversion to the respective electronic ground state (S(0)) potential energy surfaces. In addition, values of sigma(b-1,3-d-L alpha) = (3.5+/-0.2)x10(-17) cm(2) and sigma(b-1,2-d-L alpha) = (4.4+/-0.2)x10(-17) cm(2) for the previously unknown Lyman-alpha (121.6 nm) radiation photoabsorption cross sections of buta-1,3- and buta-1,2-diene in the gas-phase were determined.

References

Jun 9, 2001·Chemico-biological Interactions·G J DollardM E Jenkin
Aug 22, 2002·Journal of the American Chemical Society·Jason C RobinsonDaniel M Neumark
Aug 31, 2004·The Journal of Chemical Physics·Xiaolan MuXueming Yang
Mar 1, 2006·International Journal of Hygiene and Environmental Health·Tiina Anttinen-KlemettiKimmo Peltonen
Oct 2, 1998·Angewandte Chemie·Klaus-Heinrich Homann

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Citations

Jan 10, 2016·The Journal of Chemical Physics·Simon P NevilleMichael S Schuurman
Jan 31, 2015·The Journal of Physical Chemistry. a·Christian SchröterThomas Schultz

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