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Definitive heat of formation of methylenimine, CH2NH, and of methylenimmonium ion, CH2NH2+, by means of W2 theory

✍ Scribed by Glênisson de Oliveira; Jan M. L. Martin; Indira K. C. Silwal; Joel F. Liebman

Publisher
John Wiley and Sons
Year
2001
Tongue
English
Weight
143 KB
Volume
22
Category
Article
ISSN
0192-8651

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✦ Synopsis

Abstract

A long‐standing controversy concerning the heat of formation of methylenimine has been addressed by means of the W2 (Weizmann‐2) thermochemical approach. Our best calculated values, Δ__H__°~f,298~(CH~2~NH) = 21.1±0.5 kcal/mol and Δ__H__°~f,298~(CH~2~NH~2~^+^) = 179.4±0.5 kcal/mol, are in good agreement with the most recent measurements but carry a much smaller uncertainty. As a byproduct, we obtain the first‐ever accurate anharmonic force field for methylenimine: upon consideration of the appropriate resonances, the experimental gas‐phase band origins are all reproduced to better than 10 cm^−1^. Consideration of the difference between a fully anharmonic zero‐point vibrational energy and B3LYP/cc‐pVTZ harmonic frequencies scaled by 0.985 suggests that the calculation of anharmonic zero‐point vibrational energies can generally be dispensed with, even in benchmark work, for rigid molecules. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1297–1305, 2001

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