An ab initio benchmark study of the H + CO --> HCO reaction

• Published in: The Journal of chemical physics Vol. 105; no. 22; p. 9921
• Main Author: Woon, D E
• Format: Journal Article
• Language: English
• Published: United States 08.12.1996
• Subjects: Astronomy - methods; Carbon Monoxide - chemistry; Chemistry, Physical - methods; Computer Simulation; Electrons; Free Radicals - chemistry; Hydrocarbons - chemistry; Hydrogen - chemistry; Models, Molecular; Software; Thermodynamics; NASA Discipline Exobiology; Non-NASA Center
• ISSN: 0021-9606
• DOI: 10.1063/1.472857

The H + CO --> HCO reaction has been characterized with correlation consistent basis sets at five levels of theory in order to benchmark the sensitivities of the barrier height and reaction ergicity to the one-electron and n-electron expansions of the electronic wave function. Single and multireference methods are compared and contrasted. The coupled cluster method RCCSD(T) was found to be in very good agreement with Davidson-corrected internally-contracted multireference configuration interaction (MRCI+Q). Second-order Moller-Plesset perturbation theory (MP2) was also employed. The estimated complete basis set (CBS) limits for the barrier height (in kcal/mol) for the five methods, including harmonic zero-point energy corrections, are MP2, 4.66; RCCSD, 4.78; RCCSD(T), 4.15; MRCI, 5.10; and MRCI+Q, 4.07. Similarly, the estimated CBS limits for the ergicity of the reaction are: MP2, -17.99; RCCSD, -13.34; RCCSD(T), -13.79; MRCI, -11.46; and MRCI+Q, -13.70. Additional basis set explorations for the RCCSD(T) method demonstrate that aug-cc-pVTZ sets, even with some functions removed, are sufficient to reproduce the CBS limits to within 0.1-0.3 kcal/mol.