ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
In the propagation step of the cationic polymerization, oxetane reacts with the protonated oxetane formed in the initiation step, with concomitant ring opening of the protonated oxetane. To describe properly bond making or bond breaking, it is necessary to use MC-SCF or CI calculations. We have carried out ab initio MODPOT/VRDDO MRD-CI calculations (by the multireference double excitation-configuration interaction technique of Buenker and Peyerimhoff into which we have also meshed a number of desirable computational options for ab initio calculations on large molecules). The CI calculations were carried out on strictly orthogonalized localized occupied and virtual orbitals in the reaction region, with the remainder of the occupied molecular orbitals being folded into an effective CI Hamiltonian. The calculated potential energy surfaces indicate that a preferred pathway for this reaction resembles an SN2 reaction with the oxygen of the oxetane attacking linearly along the C4—O direction of the protonated oxetane and inversion of the hydrogens around the C4 atom.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560320763
