Structural and geometrical isomerizations of cyclopropane. Quantum chemical and RRKM calculations

Faina Dubnikova, Assa Lifshitz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

Density functional theory and two-configuration self-consistent-field calculations were carried out to investigate the unimolecular isomerizations of cyclopropane. The calculated structural parameters and vibrational frequencies of cyclopropane are in good agreement with the measured values. Obtained structures and relative energies of the transition states for the geometrical (cis - trans) and optical isomerizations agree with previous calculations. A transition state for the structural isomerization cyclopropane → propylene was located, and its energy level and vibrational frequencies were calculated with uB3LYP/cc-pVDZ method. IRC calculations using the same method and basis set show that this transition state is connected to cyclopropane and propylene without an intermediate. The wave function of the transition state contains a contribution of ionic and biradical terms. The calculated activation energy and preexponential factor for k are in very good agreement with the experimental values. RRKM calculations of the first-order rate constant for the structural isomerization were carried out over a wide range of pressures and temperatures.

Original languageEnglish
Pages (from-to)3299-3306
Number of pages8
JournalJournal of Physical Chemistry A
Volume102
Issue number19
DOIs
StatePublished - 7 May 1998

Fingerprint

Dive into the research topics of 'Structural and geometrical isomerizations of cyclopropane. Quantum chemical and RRKM calculations'. Together they form a unique fingerprint.

Cite this