Reactions of 1S, 1D, and 3P carbon atoms with water. Oxygen abstraction and intermolecular formaldehyde generation mechanisms; An MCSCF study


ÖZKAN İ., DEDE Y.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, vol.112, no.4, pp.1165-1184, 2012 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 112 Issue: 4
  • Publication Date: 2012
  • Doi Number: 10.1002/qua.23103
  • Title of Journal : INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
  • Page Numbers: pp.1165-1184

Abstract

Reactions of singlet and triplet carbon atoms with water are explored theoretically using CASSCFMCQDPT2, CCSD, and DFT methodologies. The 1S carbons are found to be unreactive. Depending on the carbon atom generation method and the reaction medium, gas-phase C(3P) attacking water may generate CO and atomic hydrogen as the end products. Reaction paths of the C(1D) + H2O system are complicated due to the involvement of two reactive potential energy surfaces with branchings occurring along each. Modifications in product distributions for reactions taking place in condensed phases are elaborated. The decisive reaction conditions, under which the oxygen abstraction and intermolecular formaldehyde generation dominate, are suggested to clarify the discrepancy related with experimental CO observation. The findings are consistent with available experimental data on this system. Oxygen abstraction and intermolecular formaldehyde generation mechanisms suggested here are capable of serving as models for similar reactions of alcohols. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012