Fifth Stereoactive Orbital on Silicon: Relaxation of the Lowest Singlet Excited State of Octamethyltrisilane

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F12%3A00385751" target="_blank" >RIV/61388963:_____/12:00385751 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/jp3068393" target="_blank" >http://dx.doi.org/10.1021/jp3068393</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jp3068393" target="_blank" >10.1021/jp3068393</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Fifth Stereoactive Orbital on Silicon: Relaxation of the Lowest Singlet Excited State of Octamethyltrisilane

Popis výsledku v původním jazyce

We address relaxation pathways in the excited singlet states 5, of saturated molecules, specifically alkylated oligosilanes. Unlike their longer peralkylated homologues, disilanes and trisilanes do not fluoresce even at low temperatures. An examination of the S-1 potential energy surface of Si3Me8 with density functional (TDDFT, LC-TDDFT), and ab initio (RICC2, RIADC(2)) methods with TZVP basis sets revealed only extremely shallow minima in the vicinity of funnels, accounting for the absence of fluorescence, rapid internal conversion, and photoproducts. Relaxed singlet excited state structures either contain one approximately trigonal bipyramidal Si atom or two that are halfway between tetrahedral and trigonal bipyramidal. Four of the ligands are thosethat the Si atom had in the ground state. Natural bond orbital analysis suggests that the fifth one is a nonbonding hybrid orbital of the lone-pair type and size intermediate between valence and Rydberg, with an only very small occupancy

Název v anglickém jazyce

Fifth Stereoactive Orbital on Silicon: Relaxation of the Lowest Singlet Excited State of Octamethyltrisilane

Popis výsledku anglicky

We address relaxation pathways in the excited singlet states 5, of saturated molecules, specifically alkylated oligosilanes. Unlike their longer peralkylated homologues, disilanes and trisilanes do not fluoresce even at low temperatures. An examination of the S-1 potential energy surface of Si3Me8 with density functional (TDDFT, LC-TDDFT), and ab initio (RICC2, RIADC(2)) methods with TZVP basis sets revealed only extremely shallow minima in the vicinity of funnels, accounting for the absence of fluorescence, rapid internal conversion, and photoproducts. Relaxed singlet excited state structures either contain one approximately trigonal bipyramidal Si atom or two that are halfway between tetrahedral and trigonal bipyramidal. Four of the ligands are thosethat the Si atom had in the ground state. Natural bond orbital analysis suggests that the fifth one is a nonbonding hybrid orbital of the lone-pair type and size intermediate between valence and Rydberg, with an only very small occupancy

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

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2012

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

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Svazek periodika

116

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

10507-10517

Kód UT WoS článku

000310482500005

EID výsledku v databázi Scopus

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