A Quantitative Molecular Orbital Perspective of the Chalcogen Bond

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18450%2F21%3A50017902" target="_blank" >RIV/62690094:18450/21:50017902 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.202000323" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.202000323</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/open.202000323" target="_blank" >10.1002/open.202000323</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A Quantitative Molecular Orbital Perspective of the Chalcogen Bond

Popis výsledku v původním jazyce

We have quantum chemically analyzed the structure and stability of archetypal chalcogen-bonded model complexes D2Ch⋅⋅⋅A− (Ch = O, S, Se, Te; D, A = F, Cl, Br) using relativistic density functional theory at ZORA-M06/QZ4P. Our purpose is twofold: (i) to compute accurate trends in chalcogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA). At odds with the commonly accepted view of chalcogen bonding as a predominantly electrostatic phenomenon, we find that chalcogen bonds, just as hydrogen and halogen bonds, have a significant covalent character stemming from strong HOMO−LUMO interactions. Besides providing significantly to the bond strength, these orbital interactions are also manifested by the structural distortions they induce as well as the associated charge transfer from A− to D2Ch. © 2021 The Authors. Published by Wiley-VCH GmbH

Název v anglickém jazyce

A Quantitative Molecular Orbital Perspective of the Chalcogen Bond

Popis výsledku anglicky

We have quantum chemically analyzed the structure and stability of archetypal chalcogen-bonded model complexes D2Ch⋅⋅⋅A− (Ch = O, S, Se, Te; D, A = F, Cl, Br) using relativistic density functional theory at ZORA-M06/QZ4P. Our purpose is twofold: (i) to compute accurate trends in chalcogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA). At odds with the commonly accepted view of chalcogen bonding as a predominantly electrostatic phenomenon, we find that chalcogen bonds, just as hydrogen and halogen bonds, have a significant covalent character stemming from strong HOMO−LUMO interactions. Besides providing significantly to the bond strength, these orbital interactions are also manifested by the structural distortions they induce as well as the associated charge transfer from A− to D2Ch. © 2021 The Authors. Published by Wiley-VCH GmbH

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

ChemistryOpen

ISSN

2191-1363

e-ISSN

—

Svazek periodika

10

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

391-401

Kód UT WoS článku

000618696300001

EID výsledku v databázi Scopus

2-s2.0-85101181985