Premium
Ab initio calculations on the barrier height for the hydrogen addition to ethylene and formaldehyde. The importance of spin projection
Author(s) -
Sosa Carlos,
Bernhard Schlegel H.
Publication year - 1986
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.560290435
Subject(s) - chemistry , ab initio , formaldehyde , hydrogen , atomic physics , computational chemistry , electronic correlation , annihilation , molecular physics , molecule , physics , organic chemistry , quantum mechanics
Heats of reaction and barrier heights have been computed for H + CH 2 CH 2 → C 2 H 5 , H + CH 2 O → CH 3 O, and H + CH 2 O → CH 2 OH using unrestricted Hartree‐Fock and Møller–Plesset perturbation theory up to fourth order (with and without spin annihilation), using single‐reference configuration interaction, and using multiconfiguration self‐consistent field methods with 3‐21G, 6‐31G(d), 6‐31G(d,p), and 6‐311G(d,p) basis sets. The barrier height in all three reactions appears to be relatively insensitive to the basis sets, but the heats of reaction are affected by p‐type polarization functions on hydrogen. Computation of the harmonic vibrational frequencies and infrared intensities with two sets of polarization functions on heavy atoms [6‐31G(2d)] improves the agreement with experiment. The experimental barrier height for H + C 2 H 4 (2.04 ± 0.08 kcal/mol) is overestimated by 7‒9 kcal/mol at the MP2, MP3, and MP4 levels. MCSCF and CISD calculations lower the barrier height by approximately 4 kcal/mol relative to the MP4 calculations but are still almost 4 kcal/mol too high compared to experiment. Annihilation of the largest spin contaminant lowers the MP4SDTQ computed barrier height by 8‒9 kcal/mol. For the hydrogen addition to formaldehyde, the same trends are observed. The overestimation of the barrier height with Møller‐Plesset perdicted barrier heights for H + C 2 H 4 → C 2 H 5 , H + CH 2 O → CH 3 O, and H + CH 2 O → CH 2 OH at the MP4SDTQ /6‐31G(d) after spin annihilation are respectively 1.8, 4.6, and 10.5 kcal/mol.