Five Stereoactive Orbitals on Silicon: Charge and Spin Localization in the n-Si4Me10-center dot Radical Anion by Trigonal Bipyramidalization
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F13%3A00394749" target="_blank" >RIV/61388963:_____/13:00394749 - isvavai.cz</a>
Výsledek na webu
<a href="http://dx.doi.org/10.1021/jz400417k" target="_blank" >http://dx.doi.org/10.1021/jz400417k</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jz400417k" target="_blank" >10.1021/jz400417k</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Five Stereoactive Orbitals on Silicon: Charge and Spin Localization in the n-Si4Me10-center dot Radical Anion by Trigonal Bipyramidalization
Popis výsledku v původním jazyce
RIUMP2/def2-TZVPPD calculations show that in addition to its usual conformation with charge and spin delocalized over the Si backbone, the isolated Si4Me10-center dot radical anion also has isomeric conformations with localized charge and spin. A structure with localization on a terminal Si atom has been examined in detail. In vacuum, it is calculated to lie 11.5 kcal/mol higher in energy than the charge-and-spin delocalized conformation, and in water the difference is as little as 1.6 kcal/mol. According to natural orbital and localized orbital analyses, the charge-and-spin-carrying terminal Si atom uses five stereoactive hybrid orbitals in a trigonal bipyramidal geometry. Four are built mostly from 3s and 3p atomic orbitals (AOs) and are used to attach a Si-3(CH3)(7) and three CH3 groups, whereas the larger equatorial fifth orbital is constructed from 4s and 4p AOs and acts as a nonbonding (radical) hybrid orbital with an occupancy of about 0.65 e.
Název v anglickém jazyce
Five Stereoactive Orbitals on Silicon: Charge and Spin Localization in the n-Si4Me10-center dot Radical Anion by Trigonal Bipyramidalization
Popis výsledku anglicky
RIUMP2/def2-TZVPPD calculations show that in addition to its usual conformation with charge and spin delocalized over the Si backbone, the isolated Si4Me10-center dot radical anion also has isomeric conformations with localized charge and spin. A structure with localization on a terminal Si atom has been examined in detail. In vacuum, it is calculated to lie 11.5 kcal/mol higher in energy than the charge-and-spin delocalized conformation, and in water the difference is as little as 1.6 kcal/mol. According to natural orbital and localized orbital analyses, the charge-and-spin-carrying terminal Si atom uses five stereoactive hybrid orbitals in a trigonal bipyramidal geometry. Four are built mostly from 3s and 3p atomic orbitals (AOs) and are used to attach a Si-3(CH3)(7) and three CH3 groups, whereas the larger equatorial fifth orbital is constructed from 4s and 4p AOs and acts as a nonbonding (radical) hybrid orbital with an occupancy of about 0.65 e.
Klasifikace
Druh
J<sub>x</sub> - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)
CEP obor
CF - Fyzikální chemie a teoretická chemie
OECD FORD obor
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Návaznosti výsledku
Projekt
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Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2013
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Journal of Physical Chemistry Letters
ISSN
1948-7185
e-ISSN
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Svazek periodika
4
Číslo periodika v rámci svazku
10
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
5
Strana od-do
1649-1653
Kód UT WoS článku
000321793800012
EID výsledku v databázi Scopus
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