Abstract
The potential energy surfaces associated with the reactions of chromium oxide cation (CrO+) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr+ via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO+ can activate carbon - carbon bonds, a reaction pathway involving C - ond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree - k orbitals is also discussed.
Original language | English (US) |
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Pages (from-to) | 1134-1143 |
Number of pages | 10 |
Journal | Journal of Physical Chemistry A |
Volume | 114 |
Issue number | 2 |
DOIs | |
State | Published - Jan 21 2010 |
Externally published | Yes |