Why do disilanes fail to fluoresce?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F11%3A00376088" target="_blank" >RIV/61388963:_____/11:00376088 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1135/cccc2011179" target="_blank" >http://dx.doi.org/10.1135/cccc2011179</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1135/cccc2011179" target="_blank" >10.1135/cccc2011179</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Why do disilanes fail to fluoresce?

Popis výsledku v původním jazyce

In contrast to longer peralkylated oligosilanes, many of which fluoresce efficiently, disilanes and trisilanes exhibit no detectable fluorescence even at low temperatures. This is especially striking in the case of disilanes, whose S-1-S-0 transition isquite strongly allowed, and which must have very efficient electronic excited state deactivation mechanisms. To identify them, we examine the lowest excited singlet state potential energy surface S-1 of Si2Me6 with TDDFT (B3LYP/TZVP, PBE0/TZVP and BHLYP/TZVP) and ab initio (RICC2/TZVP and RIADC(2)/TZVP) methods and identify several shallow minima and nearby funnels. Relaxed excited state structures show strong valence rehybridization relative to the ground state, allowing optimal accomodation of the simultaneous presence of a negative and a positive charge in their Lewis structures. Efficient decay pathways and relations to longer oligosilanes are discussed.

Název v anglickém jazyce

Why do disilanes fail to fluoresce?

Popis výsledku anglicky

In contrast to longer peralkylated oligosilanes, many of which fluoresce efficiently, disilanes and trisilanes exhibit no detectable fluorescence even at low temperatures. This is especially striking in the case of disilanes, whose S-1-S-0 transition isquite strongly allowed, and which must have very efficient electronic excited state deactivation mechanisms. To identify them, we examine the lowest excited singlet state potential energy surface S-1 of Si2Me6 with TDDFT (B3LYP/TZVP, PBE0/TZVP and BHLYP/TZVP) and ab initio (RICC2/TZVP and RIADC(2)/TZVP) methods and identify several shallow minima and nearby funnels. Relaxed excited state structures show strong valence rehybridization relative to the ground state, allowing optimal accomodation of the simultaneous presence of a negative and a positive charge in their Lewis structures. Efficient decay pathways and relations to longer oligosilanes are discussed.

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

—

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2011

Kód důvěrnosti údajů

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

Název periodika

Collection of Czechoslovak Chemical Communications

ISSN

0010-0765

e-ISSN

—

Svazek periodika

76

Číslo periodika v rámci svazku

12

Stát vydavatele periodika

CZ - Česká republika

Počet stran výsledku

32

Strana od-do

2085-2116

Kód UT WoS článku

000299816100040

EID výsledku v databázi Scopus

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