Applications of Normal Coordinates of Internal Vibrations to Generate Perturbed Structures: Dynamic Behavior of Weak to Strong Interactions Elucidated by Atoms-in-Molecules Dual Functional Analysis

• Waro Nakanishi

  Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University

• Satoko Hayashi

  Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University

• Kohei Matsuiwa

  Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University

• Masayuki Kitamoto

  Department of Material Science and Chemistry, Faculty of Systems Engineering, Wakayama University

Abstract

Normal coordinates of internal vibrations (NIV) are employed to generate the perturbed structures necessary in the atoms-in-molecules (AIM) dual functional analysis for a wide range of weak to strong interactions. Hb(rc) are plotted versus Hb(rc) − Vb(rc)/2 [= (2/8m)∇2ρb(rc)] at bond critical points in the treatment, which incorporates the classification of interactions by signs of ∇2ρb(rc) and Hb(rc). The plots are analyzed using the polar (R, θ) representation. Each plot for an interaction shows a specific curve, which is expressed by (θp, κp): θp corresponds to the tangent line for the plot measured from the y-direction and κp is the curvature. While (R, θ) correspond to the static behavior of interactions at the fully optimized structures, (θp, κp) exhibit the dynamic nature. The (θp, κp) values evaluated employing the perturbed structures with NIV are shown to be very close to those obtained using perturbed structures partially optimized with the distances in question being fixed suitably (POM). The magnitudes of differences in θp and κp between those evaluated with NIV and POM are ≤2° and ≤2 au−1, respectively, for usual interactions. It is demonstrated that NIV is applicable to wide range of usual interactions, as well as POM.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 85 (12), 1293-1305, 2012-12

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360565169050272256
• NII Article ID: 130004153009
• DOI: 10.1246/bcsj.20110377
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/85/12/1293/56274405/bcsj.20110377.pdf
• Data Source:
  • Crossref
  • CiNii Articles
  • KAKEN