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Triazene proton affinities: A comparison between density functional, Hartree–Fock, and post‐Hartree–Fock methods
Author(s) -
Schmiedekamp Ann M.,
Topol Igor A.,
Burt Stanley K.,
Razafinjanahary Holy,
Chermette Henry,
Pfaltzgraff Timothy,
Michejda Christopher J.
Publication year - 1994
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540150809
Subject(s) - triazene , chemistry , basis set , density functional theory , hartree–fock method , computational chemistry , affinities , protonation , proton , proton affinity , electron affinity (data page) , hybrid functional , quantum mechanics , physics , molecule , stereochemistry , ion , organic chemistry
The consistency of three density functional computational implementations (DMol, DGauss, and deMon) are compared with high‐level Hartree–Fock and Møller–Plesset (MP) calculations for triazene (HNNNH 2 ) and formyl triazene (HNNNHCOH). Proton affinities on all electronegative sites are investigated as well as the geometries of the neutral and protonated species. Density functional calculations employing the nonlocal gradient corrections show agreement with MP calculations for both proton affinities and geometries of neutral and protonated triazenes. Local spin density approximation DMol calculations using numerical basis sets must employ an extended basis to agree with other density functional codes using analytic Gaussian basis sets. The lowest energy conformation of triazene was found to be nonplanar; however, the degree of nonplanarity, as well as some bond lengths, is dependent on the basis set, electron correlation treatment, and methods used for the calculation. © 1994 by John Wiley & Sons, Inc. This article is a U.S. Government work and, as such, is in the public domain in the United States of America.