Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F02%3A00006521" target="_blank" >RIV/00216224:14310/02:00006521 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block

Popis výsledku v původním jazyce

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

Název v anglickém jazyce

Electron-Rich Three-Center Bonding: The Role of s,p Interactions Across the p-Block

Popis výsledku anglicky

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

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2002

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

J. Am. Chem. Soc.

ISSN

0002-7863

e-ISSN

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Svazek periodika

124

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

4787

Kód UT WoS článku

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EID výsledku v databázi Scopus

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