Linkage Isomerization via Geminate Cage or Bimolecular Mechanisms: Time-Resolved Investigations of an Organometallic Photochrome.

The extent of the photoinitiated linkage isomerization of dicarbonyl(3-cyanomethylpyridine-κN)(η(5)-methylcyclopentadienyl)manganese (4) to dicarbonyl(3-cyano-κN-methylpyridine)(η(5)-methylcyclopentadienyl)manganese (5) was examined by time-resolved infrared spectroscopy on picosecond to microsecond time scales in room temperature isooctane to determine the extent the isomerization occurs as a geminate cage rearrangement. We previously reported that a substantial part of the conversion between 4 and 5 must be a bimolecular reaction between a solvent coordinated dicarbonyl(η(5)-methylcyclopentadienyl)manganese (3) and uncoordinated 3-cyanomethylpyridine. For the purpose of designing a molecular device, it would be desirable for the photoisomerization to occur in a geminate cage reaction, because the faster the isomerization, the less opportunity for side reactions to occur.

Effusive molecular beam study of C2H6 dissociation on Pt(111).

The dissociative sticking coefficient for C2H6 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. A microcanonical unimolecular rate theory (MURT) model of the reactive system is used to extract transition state properties from the data as well as to compare our data directly with supersonic molecular beam and thermal equilibrium sticking measurements. We report for the first time the threshold energy for dissociation, E0 = 26.

Using effusive molecular beams and microcanonical unimolecular rate theory to characterize CH4 dissociation on Pt(111).

The dissociative sticking coefficient for CH4 on Pt(111) has been measured as a function of both gas temperature (Tg) and surface temperature (Ts) using effusive molecular beam and angle-integrated ambient gas dosing methods. The experimental results are used to optimize the three parameters of a microcanonical unimolecular rate theory (MURT) model of the reactive system. The MURT calculations allow us to extract transition state properties from the data as well as to compare our data directly to other molecular beam and thermal equilibrium sticking measurements.