Collisional Energy Transfer in the Multiphoton Decomposition of tert-Butyl Methyl Ether

Article abstract of DOI:10.1021/j100176a054

The multiphoton decomposition (MPD) of tert-butyl methyl ether was studied with a 100-ns pulsed CO2 laser operating on the 9R(20) line and at a fluence of 12 J/cm².For TBME pressures up to 2.7 kPa, MPD gave the following products: 2-methylpropene (TMP), methanol, 2-methyl-2-butene, acetone, methane, hydrogen, ethene, and ethane.The products result from reactions among the species produced through two channels: (1) TMP + methanol; (2) acetone + 2 CH3.A collision-dependent reaction scheme is presented to explain the pressure dependence of the MPD.In this instance, significant energy transfer between two laser-excited TBME molecules occurs before decomposition takes place.The decomposition products deactivate excited TBME molecules and reduce subsequent decomposition.