10.1021/jp803152g.s008
Marta Araujo
Marta
Araujo
Benjamin Lasorne
Benjamin
Lasorne
Michael J. Bearpark
Michael J.
Bearpark
Michael A. Robb
Michael A.
Robb
The Photochemistry of Formaldehyde: Internal Conversion and Molecular Dissociation in a Single Step?
American Chemical Society
2008
intersection space
C 1CoIn
seam
saddle point
conical intersection geometries
conversion
dissociation
nonadiabatic reaction path
CO
Molecular Dissociation
Internal Conversion
9 orbitals
H 2
nonadiabatic mechanism
2008-08-21 00:00:00
Media
https://acs.figshare.com/articles/media/The_Photochemistry_of_Formaldehyde_Internal_Conversion_and_Molecular_Dissociation_in_a_Single_Step_/2919217
A novel, nonadiabatic reaction path for H<sub>2</sub> + CO molecular dissociation of formaldehyde via an extended S<sub>1</sub>/S<sub>0</sub> conical intersection seam has been mapped out using the CAS-SCF method with a full valence active space (10 electrons, 9 orbitals). Two conical intersection geometries have been optimized, CsCoIn, a saddle point in the intersection space, and C1CoIn, which is the lowest-energy crossing point. A minimum-energy path connecting these points along a seam has also been characterized. In addition to the conventional and “roaming-atom” mechanismswhere internal conversion takes place before ground-state dissociationwe suggest that a strictly nonadiabatic mechanism can operate, where internal conversion and dissociation take place in concert.