Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F16%3A00467211" target="_blank" >RIV/61388963:_____/16:00467211 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/cphc.201600633" target="_blank" >http://dx.doi.org/10.1002/cphc.201600633</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cphc.201600633" target="_blank" >10.1002/cphc.201600633</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes

Popis výsledku v původním jazyce

The photophysical properties of oligosilanes show unique conformational dependence due to sigma-electron delocalization. The excited states of the SAS, AAS, and AEA conformations of peralkylated n-hexasilanes, in which the SiSiSiSi dihedral angles are controlled into a syn (S), anti (A), or eclipsed (E) conformation, were investigated by using UV absorption, magnetic circular dichroism (MCD), and linear dichroism spectroscopy. Simultaneous Gaussian fitting of all three spectra identified a minimal set of transitions and the wavenumbers, oscillator strengths, and MCD B terms in all three compounds. The results compare well with those obtained by using the symmetry- adapted-cluster configuration interaction method and almost as well with those obtained by time-dependent density functional theory with the PBE0 functional. The conformational dependence of the transition energies and other properties of free-chain permethylated n-hexasilane, n-Si6Me14, was also examined as a function of dihedral angles, and the striking effects found were attributed to avoided crossings between configurations of sigma sigma* and sigma pi* character.

Název v anglickém jazyce

Electronic Transitions in Conformationally Controlled Peralkylated Hexasilanes

Popis výsledku anglicky

The photophysical properties of oligosilanes show unique conformational dependence due to sigma-electron delocalization. The excited states of the SAS, AAS, and AEA conformations of peralkylated n-hexasilanes, in which the SiSiSiSi dihedral angles are controlled into a syn (S), anti (A), or eclipsed (E) conformation, were investigated by using UV absorption, magnetic circular dichroism (MCD), and linear dichroism spectroscopy. Simultaneous Gaussian fitting of all three spectra identified a minimal set of transitions and the wavenumbers, oscillator strengths, and MCD B terms in all three compounds. The results compare well with those obtained by using the symmetry- adapted-cluster configuration interaction method and almost as well with those obtained by time-dependent density functional theory with the PBE0 functional. The conformational dependence of the transition energies and other properties of free-chain permethylated n-hexasilane, n-Si6Me14, was also examined as a function of dihedral angles, and the striking effects found were attributed to avoided crossings between configurations of sigma sigma* and sigma pi* character.

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

—

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

ChemPhysChem

ISSN

1439-4235

e-ISSN

—

Svazek periodika

17

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

3010-3022

Kód UT WoS článku

000386790100011

EID výsledku v databázi Scopus

2-s2.0-84989950801