Pure through-bond state in organic molecules for analysis of the relationship between intramolecular interactions and total energy

Yuuichi Orimoto, Yuriko Aoki

    Research output: Contribution to journalArticlepeer-review

    9 Citations (Scopus)

    Abstract

    Ab initio configuration interaction through-space/bond interaction analysis was proposed for the examination of specific intramolecular interactions including the effect of electron correlations. To test the effectiveness of our method, we applied it to rotational barrier in ethane. The results of our test suggest that the insensitivity of the ethane barrier to geometric relaxations is intimately connected with the cancellation of interactions through orbital overlaps and other factors. The orbital overlaps include exchange repulsion and hyperconjugation; other factors include classic Coulomb interaction and changes in bond orbital energy. The rotational state without the barrier (pure through-bond state) can be achieved by deleting not only the "vicinal" interactions between the C-H bonds that belong to different methyl groups but also the "geminal" interactions within the methyl groups. Our mixing analysis of molecular orbitals supports the superiority of the staggered conformer by hyperconjugation. Moreover, it was demonstrated that our treatment could be applied to excited states as well as to the ground state, including electron correlation effects.

    Original languageEnglish
    Pages (from-to)355-366
    Number of pages12
    JournalInternational Journal of Quantum Chemistry
    Volume92
    Issue number4
    DOIs
    Publication statusPublished - Apr 15 2003

    All Science Journal Classification (ASJC) codes

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

    Fingerprint Dive into the research topics of 'Pure through-bond state in organic molecules for analysis of the relationship between intramolecular interactions and total energy'. Together they form a unique fingerprint.

    Cite this