@article {Chao20117154,
	title = {Molecular elimination of methyl formate in photolysis at 234 nm: Roaming vs. transition state-type mechanism},
	journal = {Physical Chemistry Chemical Physics},
	volume = {13},
	number = {15},
	year = {2011},
	note = {<p>cited By 21</p>
},
	pages = {7154-7161},
	abstract = {<p>Ion imaging coupled with (2 + 1) resonance-enhanced multiphoton ionization (REMPI) technique is employed to probe CO(v" = 0) fragments at different rotational levels following photodissociation of methyl formate (HCOOCH 3) at 234 nm. When the rotational level, J"CO, is larger than 24, only a broad translational energy distribution extending beyond 70 kcal mol-1 with an average energy of about 23 kcal mol -1 appears. The dissociation process is initiated on the energetic ground state HCOOCH3 that surpasses a tight transition state along the reaction coordinate prior to breaking into CO + CH3OH. This molecular dissociation pathway accounts for the CO fragment with larger rotational energy and large translational energy. As J"CO decreases, a bimodal distribution arises with one broad component and the other sharp component carrying the average energy of only 1-2 kcal mol-1. The branching ratio of the sharp component increases with a decrease of J"CO; (7.3 {\textpm} 0.6)\% is reached as the image is probed at J"CO = 10. The production of a sharp component is ascribed to a roaming mechanism that has the following features: a small total translational energy, a low rotational energy partitioning in CO, but a large internal energy in the CH3OH co-product. The internal energy deposition in the fragments shows distinct difference from those via the conventional transition state. {\textcopyright} the Owner Societies 2011.</p>
},
	doi = {10.1039/c0cp02710c},
	url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84859755272\&doi=10.1039\%2fc0cp02710c\&partnerID=40\&md5=f9b74194dca995352a60ad2537c49019},
	author = {Chao, M.-H. and Tsai, P.-Y. and Lin, K.-C.}
}
