TY - JOUR
T1 - Isomerisation of deuterated cyclopropanes -The possibility for stereochemical control
AU - Bolton, Kim
AU - Hase, William L.
AU - Doubleday, Charles
PY - 1997
Y1 - 1997
N2 - The direct dynamics technique, based on an AMI semiempirical Hamiltonian modified with specific reaction path parameters, has been employed to study the constant energy and thermal isomerisation of S,S-rra/i5-cyclopropane-l,2-d2 and cyclopropane-l,2,3-d3. At a classical energy of 48.25 kcal mol-1 above the conrotatory saddle point, the dynamics is mode specific. This raises the possibility of stereochemical control in this energy regime. The sensitivity of the reaction mechanism to the character of the excited normal mode eigenvector is also apparent under thermal conditions at 695 K. Similar product branching ratios are obtained for the d2 and d3 species at this temperature, when the trajectories are initialised at the conrotatory saddle point.
AB - The direct dynamics technique, based on an AMI semiempirical Hamiltonian modified with specific reaction path parameters, has been employed to study the constant energy and thermal isomerisation of S,S-rra/i5-cyclopropane-l,2-d2 and cyclopropane-l,2,3-d3. At a classical energy of 48.25 kcal mol-1 above the conrotatory saddle point, the dynamics is mode specific. This raises the possibility of stereochemical control in this energy regime. The sensitivity of the reaction mechanism to the character of the excited normal mode eigenvector is also apparent under thermal conditions at 695 K. Similar product branching ratios are obtained for the d2 and d3 species at this temperature, when the trajectories are initialised at the conrotatory saddle point.
KW - Chemical kinetics
KW - Computer experiments
KW - Energy transfer
KW - Intramolecular vibrational energy redistribution
KW - Unimolecular reactions
UR - http://www.scopus.com/inward/record.url?scp=0000008948&partnerID=8YFLogxK
U2 - 10.1002/bbpc.19971010314
DO - 10.1002/bbpc.19971010314
M3 - Article
AN - SCOPUS:0000008948
SN - 0940-483X
VL - 101
SP - 414
EP - 422
JO - Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics
JF - Berichte der Bunsengesellschaft/Physical Chemistry Chemical Physics
IS - 3
ER -