Study of the C(3P) + OH(X2Pi) --> CO(X1Sigma(g)+) + H(2S) reaction: a fully global ab initio potential energy surface of the X2A' state. 2006

Alexandre Zanchet, and Beatrice Bussery-Honvault, and Pascal Honvault
Laboratoire PALMS, UMR CNRS 6627, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France.

The C((3)P) + OH(X (2)Pi) --> CO(X (1)Sigma(g)(+)) + H((2)S) reaction has been investigated by ab initio electronic structure calculations of the X(2)A' state based on the multireference (MR) internally contracted single and double configuration interaction (SDCI) method plus Davidson correction (+Q) using Dunning aug-cc-pVQZ basis sets. In particular, the multireference space is taken to be a complete active space (CAS). Improvement over previously proposed potential energy surfaces for HCO/COH is obtained in the sense that present surface describes also the potential part where the CO interatomic distance is large. A large number of geometries (around 2000) have been calculated and analytically fitted using the reproducing kernel Hilbert space (RKHS) method of Ho and Rabitz both for the two-body and three-body terms following the many-body decomposition of the total electronic energies. Results show that the global reaction is highly exothermic ( approximately 6.4 eV) and barrierless (relative to the reactant channel), while five potential barriers are located on this surface. The three minima and five saddle points observed are characterized and found to be in good agreement with previous work. The three minima correspond to the formation of HCO and COH complexes and to the CO + H products, with the COH complex being a metastable minimum relative to the product channel. The five saddle points correspond to potential barriers for both the dissociation/formation of HCO and COH into/from CO + H, to barriers for the isomerization of HCO into COH and to barriers for the inversion of HCO and COH through their respective linear configuration.

UI MeSH Term Description Entries
D008956 Models, Chemical Theoretical representations that simulate the behavior or activity of chemical processes or phenomena; includes the use of mathematical equations, computers, and other electronic equipment. Chemical Models,Chemical Model,Model, Chemical
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D002244 Carbon A nonmetallic element with atomic symbol C, atomic number 6, and atomic weight [12.0096; 12.0116]. It may occur as several different allotropes including DIAMOND; CHARCOAL; and GRAPHITE; and as SOOT from incompletely burned fuel. Carbon-12,Vitreous Carbon,Carbon 12,Carbon, Vitreous
D002248 Carbon Monoxide Carbon monoxide (CO). A poisonous colorless, odorless, tasteless gas. It combines with hemoglobin to form carboxyhemoglobin, which has no oxygen carrying capacity. The resultant oxygen deprivation causes headache, dizziness, decreased pulse and respiratory rates, unconsciousness, and death. (From Merck Index, 11th ed) Monoxide, Carbon
D004735 Energy Transfer The transfer of energy of a given form among different scales of motion. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed). It includes the transfer of kinetic energy and the transfer of chemical energy. The transfer of chemical energy from one molecule to another depends on proximity of molecules so it is often used as in techniques to measure distance such as the use of FORSTER RESONANCE ENERGY TRANSFER. Transfer, Energy
D006859 Hydrogen The first chemical element in the periodic table with atomic symbol H, and atomic number 1. Protium (atomic weight 1) is by far the most common hydrogen isotope. Hydrogen also exists as the stable isotope DEUTERIUM (atomic weight 2) and the radioactive isotope TRITIUM (atomic weight 3). Hydrogen forms into a diatomic molecule at room temperature and appears as a highly flammable colorless and odorless gas. Protium,Hydrogen-1
D006878 Hydroxides Inorganic compounds that contain the OH- group.
D013499 Surface Properties Characteristics or attributes of the outer boundaries of objects, including molecules. Properties, Surface,Property, Surface,Surface Property

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