| Description: | This article discusses oxygen atom transfer energetics. Several density functional methods, the semiempirical methods AM1 and PM3, Hartree-Fock, and Gaussian3 theories were applied to compute the oxygen atom transfer enthalpies for 14 X/XO couples (inorganic and organic systems, charged and neutral species, light and heavy main group element containing molecules). The calculated reaction enthalpies were compared to available experimental data. The G3 method alone was found to perform within the experimental error, while the popular B3LYP and BLYP functionals provided inadequate results. Solvent effects were estimated for 19 neutral and anionic X/XO couples by using the conductor-like polarizable continuum model and several cavity models coupled with the B3LYP/6-31++G-(2d,2p) level of theory. Surprisingly, the magnitude of the aqueous solvent correction was found to vary significantly for different solute cavity models, occasionally giving larger errors than the gas-phase calculation. |
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| Creator(s): | |
| Creation Date: | February 23, 2006 |
| Partner(s): |
UNT College of Arts and Sciences
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| Collection(s): |
UNT Scholarly Works
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| Usage: |
Total Uses: 60
Past 30 days: 3
Yesterday: 0
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| Creator (Author): |
Dinescu, Adriana
University of North Texas |
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| Creator (Author): |
Whiteley, Clinton
University of North Texas |
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| Creator (Author): |
Combs, Rachel R.
University of North Texas |
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| Creator (Author): |
Cundari, Thomas R., 1964-
University of North Texas |
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| Publisher Info: |
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
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| Original Creation Date: | February 23, 2006 | |
| Description: | This article discusses oxygen atom transfer energetics. Several density functional methods, the semiempirical methods AM1 and PM3, Hartree-Fock, and Gaussian3 theories were applied to compute the oxygen atom transfer enthalpies for 14 X/XO couples (inorganic and organic systems, charged and neutral species, light and heavy main group element containing molecules). The calculated reaction enthalpies were compared to available experimental data. The G3 method alone was found to perform within the experimental error, while the popular B3LYP and BLYP functionals provided inadequate results. Solvent effects were estimated for 19 neutral and anionic X/XO couples by using the conductor-like polarizable continuum model and several cavity models coupled with the B3LYP/6-31++G-(2d,2p) level of theory. Surprisingly, the magnitude of the aqueous solvent correction was found to vary significantly for different solute cavity models, occasionally giving larger errors than the gas-phase calculation. |
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| Degree: |
Department:
Chemistry
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| Note: |
Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2006 American Chemical Society. |
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| Physical Description: |
4 p. |
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| Keyword(s): | density functional methods | oxygen atom transfer energetics | |
| Source: | Journal of Physical Chemistry A, 2006, Washington DC: American Chemical Society, pp. 4053-4056 | |
| Partner: |
UNT College of Arts and Sciences
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| Collection: |
UNT Scholarly Works
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| Identifier: |
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| Resource Type: | Article | |
| Format: | Text | |
| Rights: |
Access:
Public
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| Citation: |
Publication Title: Journal of Physical Chemistry A
Volume: 110
Page Start: 4053
Page End: 4056
Pages: 4
Peer Reviewed: Yes
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