Journal article

Publication year: 2014

Pages: 2801-2809

Journal: The Journal of Physical Chemistry A

Volume number: 118

Issue number: 15

DOI Link: https://doi.org/10.1021/jp501107b

Publisher: American Chemical Society

Abstract: 

Car–Parrinello molecular dynamics was used to explore the reactions
between triplet and singlet carbon atoms with benzene. The computations
reveal that, in the singlet C atom reaction, products are very
exothermic where nearly every collision yields a product that is
determined by the initial encounter geometry. The singlet C atom
reaction does not follow the minimum energy path because the bimolecular
reaction is controlled by dynamics (i.e., initial orientation of
encounter). On the other hand, in a 10 K solid Ar matrix, ground state
C(³P) atoms do tend to follow RRKM kinetics. Thus, ab initio
molecular dynamics (AIMD) results indicate that a significant fraction
of C–H insertion occurs to form phenylcarbene whereas, in marked
contrast to previous theoretical and experimental conclusions, the Ar
matrix isolation studies indicate a large fraction of direct
cycloheptatetraene formation, without the intermediacy of phenylcarbene.
The AIMD calculations are more consistent with vaporized carbon atom
experiments where labeling studies indicate the initial formation of
phenylcarbene. This underlines that the availability of thermodynamic
sinks can completely alter the observed reaction dynamics.

Harvard Citation style: McKee, M., Reisenauer, H. and Schreiner, P. (2014) Combined ab Initio Molecular Dynamics and Experimental Studies of Carbon Atom Addition to Benzene, The Journal of Physical Chemistry A, 118(15), pp. 2801-2809. https://doi.org/10.1021/jp501107b

APA Citation style: McKee, M., Reisenauer, H., & Schreiner, P. (2014). Combined ab Initio Molecular Dynamics and Experimental Studies of Carbon Atom Addition to Benzene. The Journal of Physical Chemistry A. 118(15), 2801-2809. https://doi.org/10.1021/jp501107b