Proton affinities of molecules containing nitrogen and oxygen: comparing ab initio and semiempirical results to experiments

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Abstract

We report a comparison of theoretical and experimental proton affinities at nitrogen and oxygen sites within a series of small molecules. The calculated proton affinities are determined using the semiempirical methods AM1, MNDO, and PM3; the ab initio Hartree–Fock method at the following basis levels: 3‐21G//3‐21G, 3‐21+G//3‐21G, 6‐31G*//6‐31G*, and 6‐31+G(d, p)//6‐31G*; and Møller–Plesset perturbation calculations: MP2/6‐31G*//6‐31G*, MP3/6‐31G*//6‐31G*, MP2/6‐31G+(d, p)//6‐31G*, MP3/6‐31G+(d, p)//6‐31G*, and MP4(SDTQ)/6‐31G+G(d, p)//6‐31G*. The semiempirical methods have more nonsystematic scatter from the experimental values, compared to even the minimal 3‐21G level ab initio calculations. The thermodynamically corrected 6‐31G*//6‐31G* proton affinities provide acceptable results compared to experiment, and we see no significant improvement over 6‐31G*//6‐31G* in the proton affinities with any of the higher‐level calculations. © 1992 John Wiley & Sons, Inc.

Original languageEnglish (US)
Pages (from-to)783-800
Number of pages18
JournalInternational Journal of Quantum Chemistry
Volume43
Issue number6
DOIs
StatePublished - Jan 1 1992

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affinity
Protons
Nitrogen
Oxygen
nitrogen
Molecules
protons
oxygen
molecules
Experiments
perturbation

All Science Journal Classification (ASJC) codes

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

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title = "Proton affinities of molecules containing nitrogen and oxygen: comparing ab initio and semiempirical results to experiments",
abstract = "We report a comparison of theoretical and experimental proton affinities at nitrogen and oxygen sites within a series of small molecules. The calculated proton affinities are determined using the semiempirical methods AM1, MNDO, and PM3; the ab initio Hartree–Fock method at the following basis levels: 3‐21G//3‐21G, 3‐21+G//3‐21G, 6‐31G*//6‐31G*, and 6‐31+G(d, p)//6‐31G*; and M{\o}ller–Plesset perturbation calculations: MP2/6‐31G*//6‐31G*, MP3/6‐31G*//6‐31G*, MP2/6‐31G+(d, p)//6‐31G*, MP3/6‐31G+(d, p)//6‐31G*, and MP4(SDTQ)/6‐31G+G(d, p)//6‐31G*. The semiempirical methods have more nonsystematic scatter from the experimental values, compared to even the minimal 3‐21G level ab initio calculations. The thermodynamically corrected 6‐31G*//6‐31G* proton affinities provide acceptable results compared to experiment, and we see no significant improvement over 6‐31G*//6‐31G* in the proton affinities with any of the higher‐level calculations. {\circledC} 1992 John Wiley & Sons, Inc.",
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N2 - We report a comparison of theoretical and experimental proton affinities at nitrogen and oxygen sites within a series of small molecules. The calculated proton affinities are determined using the semiempirical methods AM1, MNDO, and PM3; the ab initio Hartree–Fock method at the following basis levels: 3‐21G//3‐21G, 3‐21+G//3‐21G, 6‐31G*//6‐31G*, and 6‐31+G(d, p)//6‐31G*; and Møller–Plesset perturbation calculations: MP2/6‐31G*//6‐31G*, MP3/6‐31G*//6‐31G*, MP2/6‐31G+(d, p)//6‐31G*, MP3/6‐31G+(d, p)//6‐31G*, and MP4(SDTQ)/6‐31G+G(d, p)//6‐31G*. The semiempirical methods have more nonsystematic scatter from the experimental values, compared to even the minimal 3‐21G level ab initio calculations. The thermodynamically corrected 6‐31G*//6‐31G* proton affinities provide acceptable results compared to experiment, and we see no significant improvement over 6‐31G*//6‐31G* in the proton affinities with any of the higher‐level calculations. © 1992 John Wiley & Sons, Inc.

AB - We report a comparison of theoretical and experimental proton affinities at nitrogen and oxygen sites within a series of small molecules. The calculated proton affinities are determined using the semiempirical methods AM1, MNDO, and PM3; the ab initio Hartree–Fock method at the following basis levels: 3‐21G//3‐21G, 3‐21+G//3‐21G, 6‐31G*//6‐31G*, and 6‐31+G(d, p)//6‐31G*; and Møller–Plesset perturbation calculations: MP2/6‐31G*//6‐31G*, MP3/6‐31G*//6‐31G*, MP2/6‐31G+(d, p)//6‐31G*, MP3/6‐31G+(d, p)//6‐31G*, and MP4(SDTQ)/6‐31G+G(d, p)//6‐31G*. The semiempirical methods have more nonsystematic scatter from the experimental values, compared to even the minimal 3‐21G level ab initio calculations. The thermodynamically corrected 6‐31G*//6‐31G* proton affinities provide acceptable results compared to experiment, and we see no significant improvement over 6‐31G*//6‐31G* in the proton affinities with any of the higher‐level calculations. © 1992 John Wiley & Sons, Inc.

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