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Reactions of 1 S, 1 D, and 3 P carbon atoms with water. Oxygen abstraction and intermolecular formaldehyde generation mechanisms; An MCSCF study
Author(s) -
Ozkan Ilker,
Dede Yavuz
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23103
Subject(s) - chemistry , intermolecular force , formaldehyde , hydrogen atom abstraction , singlet oxygen , computational chemistry , carbon fibers , oxygen , hydrogen atom , hydrogen , photochemistry , singlet state , atom (system on chip) , chemical physics , molecule , atomic physics , organic chemistry , materials science , excited state , physics , alkyl , composite number , composite material , computer science , embedded system
Reactions of singlet and triplet carbon atoms with water are explored theoretically using CASSCF–MCQDPT2, CCSD, and DFT methodologies. The 1 S carbons are found to be unreactive. Depending on the carbon atom generation method and the reaction medium, gas‐phase C( 3 P) attacking water may generate CO and atomic hydrogen as the end products. Reaction paths of the C( 1 D) + H 2 O 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. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012