Charge localization in alcohol isomers studied by Compton scattering

M. Hakala, K. Nygård, J. Vaara, M. Itou, Y. Sakurai, K. Hämäläinen

    Research output: Contribution to journalArticleScientificpeer-review

    Abstract

    The isomers of small molecule alcohols propanol (PrOH) and butanol (BuOH) are studied by x-ray Compton scattering experiments with synchrotron radiation and density-functional theory calculations. The lineshape of the measured spectra, i.e., the Compton profile, is a momentum-space property, and its changes reflect changes in the electronic charge density between the isomers. Compared to the linear alcohols (n-PrOH and n-BuOH), the Compton profiles of the branched alcohols (iso-PrOH, iso-BuOH, sec-BuOH) are found to be narrower, which indicates a more delocalized charge for the latter. The calculations are performed for systems consisting of one to three monomer units and are found to reproduce reasonably the experimental spectral features. The influence of the basis set and exchange-correlation scheme is studied in more detail. The results provide new insight into the isomeric differences in small molecule alcohols and show that quantum chemical calculations can be increasingly tested against the x-ray Compton scattering data.
    Original languageEnglish
    JournalJournal of Chemical Physics
    Volume130
    Issue number3
    Pages (from-to)034506-1-034506-8
    Number of pages8
    ISSN0021-9606
    DOIs
    Publication statusPublished - 2009
    MoE publication typeA1 Journal article-refereed

    Fields of Science

    • 114 Physical sciences

    Cite this

    Hakala, M. ; Nygård, K. ; Vaara, J. ; Itou, M. ; Sakurai, Y. ; Hämäläinen, K. / Charge localization in alcohol isomers studied by Compton scattering. In: Journal of Chemical Physics. 2009 ; Vol. 130, No. 3. pp. 034506-1-034506-8.
    @article{346a53890d134a4296016a72df5b0522,
    title = "Charge localization in alcohol isomers studied by Compton scattering",
    abstract = "The isomers of small molecule alcohols propanol (PrOH) and butanol (BuOH) are studied by x-ray Compton scattering experiments with synchrotron radiation and density-functional theory calculations. The lineshape of the measured spectra, i.e., the Compton profile, is a momentum-space property, and its changes reflect changes in the electronic charge density between the isomers. Compared to the linear alcohols (n-PrOH and n-BuOH), the Compton profiles of the branched alcohols (iso-PrOH, iso-BuOH, sec-BuOH) are found to be narrower, which indicates a more delocalized charge for the latter. The calculations are performed for systems consisting of one to three monomer units and are found to reproduce reasonably the experimental spectral features. The influence of the basis set and exchange-correlation scheme is studied in more detail. The results provide new insight into the isomeric differences in small molecule alcohols and show that quantum chemical calculations can be increasingly tested against the x-ray Compton scattering data.",
    keywords = "114 Physical sciences",
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    Charge localization in alcohol isomers studied by Compton scattering. / Hakala, M.; Nygård, K.; Vaara, J.; Itou, M.; Sakurai, Y.; Hämäläinen, K.

    In: Journal of Chemical Physics, Vol. 130, No. 3, 2009, p. 034506-1-034506-8.

    Research output: Contribution to journalArticleScientificpeer-review

    TY - JOUR

    T1 - Charge localization in alcohol isomers studied by Compton scattering

    AU - Hakala, M.

    AU - Nygård, K.

    AU - Vaara, J.

    AU - Itou, M.

    AU - Sakurai, Y.

    AU - Hämäläinen, K.

    PY - 2009

    Y1 - 2009

    N2 - The isomers of small molecule alcohols propanol (PrOH) and butanol (BuOH) are studied by x-ray Compton scattering experiments with synchrotron radiation and density-functional theory calculations. The lineshape of the measured spectra, i.e., the Compton profile, is a momentum-space property, and its changes reflect changes in the electronic charge density between the isomers. Compared to the linear alcohols (n-PrOH and n-BuOH), the Compton profiles of the branched alcohols (iso-PrOH, iso-BuOH, sec-BuOH) are found to be narrower, which indicates a more delocalized charge for the latter. The calculations are performed for systems consisting of one to three monomer units and are found to reproduce reasonably the experimental spectral features. The influence of the basis set and exchange-correlation scheme is studied in more detail. The results provide new insight into the isomeric differences in small molecule alcohols and show that quantum chemical calculations can be increasingly tested against the x-ray Compton scattering data.

    AB - The isomers of small molecule alcohols propanol (PrOH) and butanol (BuOH) are studied by x-ray Compton scattering experiments with synchrotron radiation and density-functional theory calculations. The lineshape of the measured spectra, i.e., the Compton profile, is a momentum-space property, and its changes reflect changes in the electronic charge density between the isomers. Compared to the linear alcohols (n-PrOH and n-BuOH), the Compton profiles of the branched alcohols (iso-PrOH, iso-BuOH, sec-BuOH) are found to be narrower, which indicates a more delocalized charge for the latter. The calculations are performed for systems consisting of one to three monomer units and are found to reproduce reasonably the experimental spectral features. The influence of the basis set and exchange-correlation scheme is studied in more detail. The results provide new insight into the isomeric differences in small molecule alcohols and show that quantum chemical calculations can be increasingly tested against the x-ray Compton scattering data.

    KW - 114 Physical sciences

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    SP - 034506-1-034506-8

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    JF - Journal of Chemical Physics

    SN - 0021-9606

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