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Assessment of theoretical methods for the calculation of methyl cation affinities.

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Title: Assessment of theoretical methods for the calculation of methyl cation affinities.
Authors: Wei, Y.1, Singer, T.1, Mayr, H.1, Sastry, G. N.1, Zipse, H.1 zipse@cup.uni-muenchen.de
Source: Journal of Computational Chemistry. 2008, Vol. 29 Issue 2, p291-297. 7p. 2 Diagrams, 4 Charts.
Subjects: Cations, Density functionals, Organic chemistry, Carbocations, Organic bases, Chemical affinity
Abstract: The methyl cation affinity (MCA; 298 K) of a variety of neutral and anionic bases has been examined computationally with a wide variety of theoretical methods. These include high-level composite procedures such as W1, G3, G3B3, and G2, conventional ab initio methods such as CCSD(T) and MP2, as well as a selection of density functional theory (DFT) methods. Experimental results for a variety of small model systems are well reproduced with practically all these methods, and the performance of DFT based methods are far superior in comparison to their MP2 analogs for these small models. For larger model, systems including motifs frequently encountered in organocatalysts, the performance deteriorates somewhat for DFT methods, while it improves significantly for MP2, rendering the former methods unreliable for common organic bases. Thus, MP2 calculations performed in combination with basis sets such as 6-31+G(2d, p) or larger, appear to offer a practical and reliable approach to compute MCAs of organic bases. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [ABSTRACT FROM AUTHOR]
Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
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PubType: Academic Journal
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  Data: Assessment of theoretical methods for the calculation of methyl cation affinities.
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  Data: <searchLink fieldCode="AR" term="%22Wei%2C+Y%2E%22">Wei, Y.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Singer%2C+T%2E%22">Singer, T.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mayr%2C+H%2E%22">Mayr, H.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Sastry%2C+G%2E+N%2E%22">Sastry, G. N.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Zipse%2C+H%2E%22">Zipse, H.</searchLink><relatesTo>1</relatesTo><i> zipse@cup.uni-muenchen.de</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Computational+Chemistry%22">Journal of Computational Chemistry</searchLink>. 2008, Vol. 29 Issue 2, p291-297. 7p. 2 Diagrams, 4 Charts.
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  Data: <searchLink fieldCode="DE" term="%22Cations%22">Cations</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink><br /><searchLink fieldCode="DE" term="%22Organic+chemistry%22">Organic chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Carbocations%22">Carbocations</searchLink><br /><searchLink fieldCode="DE" term="%22Organic+bases%22">Organic bases</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+affinity%22">Chemical affinity</searchLink>
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  Data: The methyl cation affinity (MCA; 298 K) of a variety of neutral and anionic bases has been examined computationally with a wide variety of theoretical methods. These include high-level composite procedures such as W1, G3, G3B3, and G2, conventional ab initio methods such as CCSD(T) and MP2, as well as a selection of density functional theory (DFT) methods. Experimental results for a variety of small model systems are well reproduced with practically all these methods, and the performance of DFT based methods are far superior in comparison to their MP2 analogs for these small models. For larger model, systems including motifs frequently encountered in organocatalysts, the performance deteriorates somewhat for DFT methods, while it improves significantly for MP2, rendering the former methods unreliable for common organic bases. Thus, MP2 calculations performed in combination with basis sets such as 6-31+G(2d, p) or larger, appear to offer a practical and reliable approach to compute MCAs of organic bases. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1002/jcc.20790
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 7
        StartPage: 291
    Subjects:
      – SubjectFull: Cations
        Type: general
      – SubjectFull: Density functionals
        Type: general
      – SubjectFull: Organic chemistry
        Type: general
      – SubjectFull: Carbocations
        Type: general
      – SubjectFull: Organic bases
        Type: general
      – SubjectFull: Chemical affinity
        Type: general
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      – TitleFull: Assessment of theoretical methods for the calculation of methyl cation affinities.
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            NameFull: Wei, Y.
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            NameFull: Singer, T.
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            NameFull: Mayr, H.
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            NameFull: Sastry, G. N.
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            NameFull: Zipse, H.
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              Text: 2008
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