. . . "0002-7863" . . "This paper analyzes the importance of s,p mixing-a necessary addition to the simplest Rundle-Pimentel picture-and periodic and group trends in electron-rich three-center bonding. Our analysis proceeds through a detailed quantum chemical study of the stability of electron-rich three-center bonding in triatomic 22-valence electron anions, To provide interpretations, a perturbational molecular orbital (MO) analysis of s,p mixing is carried out. This analysis of the orbitals and the overlap populations is then tested by density functional calculations for a number of linear trihalides, trichalcogenides, and tripnictides. The most important effect of s,p mixing on the in-line bonding is in destabilization of the 3sigma(g) orbital and is determined by the overlap between the s orbital of the central atom and the p orbital of the terminal atom. Further destabilization arises from the repulsion of p, lone pairs. Both of these antibonding effects increase with increasing negative charge of the system. The stab"@en . "This paper analyzes the importance of s,p mixing-a necessary addition to the simplest Rundle-Pimentel picture-and periodic and group trends in electron-rich three-center bonding. Our analysis proceeds through a detailed quantum chemical study of the stability of electron-rich three-center bonding in triatomic 22-valence electron anions, To provide interpretations, a perturbational molecular orbital (MO) analysis of s,p mixing is carried out. This analysis of the orbitals and the overlap populations is then tested by density functional calculations for a number of linear trihalides, trichalcogenides, and tripnictides. The most important effect of s,p mixing on the in-line bonding is in destabilization of the 3sigma(g) orbital and is determined by the overlap between the s orbital of the central atom and the p orbital of the terminal atom. Further destabilization arises from the repulsion of p, lone pairs. Both of these antibonding effects increase with increasing negative charge of the system. The stab" . . "124" . . "This paper analyzes the importance of s,p mixing-a necessary addition to the simplest Rundle-Pimentel picture-and periodic and group trends in electron-rich three-center bonding. Our analysis proceeds through a detailed quantum chemical study of the stability of electron-rich three-center bonding in triatomic 22-valence electron anions, To provide interpretations, a perturbational molecular orbital (MO) analysis of s,p mixing is carried out. This analysis of the orbitals and the overlap populations is then tested by density functional calculations for a number of linear trihalides, trichalcogenides, and tripnictides. The most important effect of s,p mixing on the in-line bonding is in destabilization of the 3sigma(g) orbital and is determined by the overlap between the s orbital of the central atom and the p orbital of the terminal atom. Further destabilization arises from the repulsion of p, lone pairs. Both of these antibonding effects increase with increasing negative charge of the system. The stab"@cs . . "RIV/00216224:14310/02:00006521!RIV09-MSM-14310___" . . . . . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . "Munzarov\u00E1, Mark\u00E9ta" . . . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block"@cs . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block" . . . "J. Am. Chem. Soc." . "1"^^ . "14310" . . . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block"@en . "Z(MSM 143100011)" . . "RIV/00216224:14310/02:00006521" . "Hoffmann, Roald" . "2"^^ . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block" . "644805" . . "AB-INITIO CALCULATIONS; GAS-PHASE; POLYHALIDE ANIONS; CRYSTAL-STRUCTURE; TRIFLUORIDE ION; SOLID-STATE; ENERGY; HYPERVALENT; APPROXIMATION; STABILITY"@en . "9"^^ . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block"@cs . "17" . . "[F29A6B3977FD]" . "Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block"@en . . .