Effect of Conformation on Electron Localization and Delocalization in Infinite Helical Chains [X(CH3)2]∞ (X = Si, Ge, Sn, and Pb)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F19%3A00508874" target="_blank" >RIV/61388963:_____/19:00508874 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/jacs.9b04780" target="_blank" >https://pubs.acs.org/doi/10.1021/jacs.9b04780</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.9b04780" target="_blank" >10.1021/jacs.9b04780</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Effect of Conformation on Electron Localization and Delocalization in Infinite Helical Chains [X(CH3)2]∞ (X = Si, Ge, Sn, and Pb)

Popis výsledku v původním jazyce

An intuitive explanation of the effects of conformation (backbone dihedral angle) on electron delocalization in infinite saturated regular helices [(CH3)2]∞Si, [(CH3)2Ge]∞, [(CH3)2Sn]∞, and [(CH3)2Pb]∞ is offered in terms of the simple Ladder C model and confirmed by density functional theory calculations. The effective hole mass, which ranges from near zero to infinity as a function of conformation, is used as a measure of the degree of delocalization and relates to the effects of chain length extension in finite systems. The position of the Fermi level in reciprocal space has a simple counterpart in systems of finite length and is used to characterize the dominant mechanism, σ conjugation (geminal interactions) or σ hyperconjugation (vicinal interactions, through-bond coupling). Constructive or destructive interference of the two mechanisms produces three different delocalization regimes as a function of the backbone dihedral angle and analogy is drawn to polycyclic π-electron systems consisting of fused Hückel or Möbius four-membered rings.

Název v anglickém jazyce

Effect of Conformation on Electron Localization and Delocalization in Infinite Helical Chains [X(CH3)2]∞ (X = Si, Ge, Sn, and Pb)

Popis výsledku anglicky

An intuitive explanation of the effects of conformation (backbone dihedral angle) on electron delocalization in infinite saturated regular helices [(CH3)2]∞Si, [(CH3)2Ge]∞, [(CH3)2Sn]∞, and [(CH3)2Pb]∞ is offered in terms of the simple Ladder C model and confirmed by density functional theory calculations. The effective hole mass, which ranges from near zero to infinity as a function of conformation, is used as a measure of the degree of delocalization and relates to the effects of chain length extension in finite systems. The position of the Fermi level in reciprocal space has a simple counterpart in systems of finite length and is used to characterize the dominant mechanism, σ conjugation (geminal interactions) or σ hyperconjugation (vicinal interactions, through-bond coupling). Constructive or destructive interference of the two mechanisms produces three different delocalization regimes as a function of the backbone dihedral angle and analogy is drawn to polycyclic π-electron systems consisting of fused Hückel or Möbius four-membered rings.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

141

Číslo periodika v rámci svazku

33

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

13101-13113

Kód UT WoS článku

000482546400026

EID výsledku v databázi Scopus

2-s2.0-85071036204