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Author(s):   Becerra, R.; Goldberg, N.; Cannady, J.P.; Almond, M.J.; Ogden, J.S.; Walsh, R.
Title:   Experimental and theoretical evidence for homogeneous catalysis in the gas-phase reaction of SiH2 with H2O (and D2O): A combined kinetic and quantum chemical study
Journal:   J. Am. Chem. Soc.
Volume:   126
Page(s):   6816 - 6824
Year:   2004
Reference type:   Journal article
Squib:   2004BEC/GOL6816-6824

Reaction:   D2O + D2O + SiH2 → SiH2DOD + D2O
Reaction order:   3
Temperature:   297 K
Pressure:  1.33E-3 - 1.33E-2 bar
Rate expression:   5.4x10-30 [cm6/molecule2 s]
Bath gas:   D2O
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure dependent
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Vis-UV absorption
Comments:   Measured rate of reaction of SiH2 with H2O and D2O going onto SiH3OH. Found reaction involved complex SiH2--H2O reacting further with another H2O (or D2O). Measured at range of total pressures(0-10 torr) and two temperatures 297, 345 K. SiH2 generated by ArF excimer laser flash photolysis at 193 nm of Phenylsilane PhSiH3. SiH2 detected using single mode dye laser absorption at 17259.5 cm-1. Used ab initio and RRKM methods to confirm observation and conclusions of experimental measurements.

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