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Abstract The intrinsic dynamic and static nature mc center‐ne electron interactions of the σ‐type σ(mcc‐nee) were elucidated for the Se‐Se interactions in dicationic oligomers of Se(CH2CH2CH2)2Se (1 (Se, Se)) [n2+ (Se, Se): n=1–8], especially for mc≥6, where n2+ (Se, Se: n=1–8) are abbreviated by n2+ (n=1–8), respectively. QTAIM dual functional analysis (QTAIM‐DFA) was applied to the interactions. Perturbed structures generated using coordinates derived from the compliance constants (Cii) were employed for QTAIM‐DFA. Each Se‐*‐Se in 12+ and 22+ has the nature of CT‐TBP (trigonal bipyramidal adduct formation through CT) and Cov‐w (weak covalent), respectively, which supply the starting points of the investigations. The asterisk emphasizes the existence of a bond critical point on the interaction. All Se‐*‐Se in 32+ are classified by the regular closed shell (r‐CS) interactions and characterized as CT‐MC (molecular complex formation through CT), which are denoted as r‐CS/CT‐MC, except for the central interaction, of which nature is r‐CS/CT‐TBP. Most interactions in 42+–82+ are r‐CS/t‐HBwc (typical‐HB with covalency) but some are pure‐CS/t‐HBnc (t‐HB with no covalency). The linear Se2n2+ interactions in 22+–82+ seem close to those without any limitations, since the nature of Se‐*‐Se inside and outside of (CH2CH2CH2)2 are very similar with each other. The linear Se2n2+ interactions in 32+–82+ are shown to be analyzed as σ(mcc‐nee: 6≤mc≤16), not by the accumulated σ(3c–4e).

The intrinsic dynamic and static nature mc center-ne electron interactions of the σ-type σ(mcc-nee) were elucidated for the Se-Se interactions in dicationic oligomers of Se(CH2CH2CH2)2Se (1 (Se, Se)) [n2+ (Se, Se): n=1-8], especially for mc≥6, where n2+ (Se, Se: n=1-8) are abbreviated by n2+ (n=1-8), respectively. QTAIM dual functional analysis (QTAIM-DFA) was applied to the interactions. Perturbed structures generated using coordinates derived from the compliance constants (Cii) were employed for QTAIM-DFA. Each Se-*-Se in 12+ and 22+ has the nature of CT-TBP (trigonal bipyramidal adduct formation through CT) and Cov-w (weak covalent), respectively, which supply the starting points of the investigations. The asterisk emphasizes the existence of a bond critical point on the interaction. All Se-*-Se in 32+ are classified by the regular closed shell (r-CS) interactions and characterized as CT-MC (molecular complex formation through CT), which are denoted as r-CS/CT-MC, except for the central interaction, of which nature is r-CS/CT-TBP. Most interactions in 42+-82+ are r-CS/t-HBwc (typical-HB with covalency) but some are pure-CS/t-HBnc (t-HB with no covalency). The linear Se2n2+ interactions in 22+-82+ seem close to those without any limitations, since the nature of Se-*-Se inside and outside of (CH2CH2CH2)2 are very similar with each other. The linear Se2n2+ interactions in 32+-82+ are shown to be analyzed as σ(mcc-nee: 6≤mc≤16), not by the accumulated σ(3c-4e). [ABSTRACT FROM AUTHOR]