An ab initio benchmark study of the H + CO --> HCO reaction.
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.
Woon
D E
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Molecular Research Institute, Palo Alto, California 94304, USA.
D001256:Astronomy / Q000379:methods; D002248:Carbon Monoxide / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry*; D006838:Hydrocarbons / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D008958:Models, Molecular; D012984:Software; D013816:Thermodynamics
D005609:Free Radicals; D006838:Hydrocarbons; D002248:Carbon Monoxide; D006859:Hydrogen