Magnetic circular dichroism of an unaromatic planar [8]annulene

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F18%3A00492379" target="_blank" >RIV/61388963:_____/18:00492379 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1002/poc.3854" target="_blank" >http://dx.doi.org/10.1002/poc.3854</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/poc.3854" target="_blank" >10.1002/poc.3854</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Magnetic circular dichroism of an unaromatic planar [8]annulene

Popis výsledku v původním jazyce

An overview of magnetic circular dichroism (MCD) spectroscopy of pi-electron systems derived from a 4N-electron perimeter is provided, with emphasis on the hypothetical parent cycloocta-1,3,5,7-tetraene of D-8h symmetry (1) and its D-4h symmetry derivatives. UV-visible absorption and MCD spectra of 2, D-4h, symmetric cycloocta-1,3,5,7-tetraene planarized by the effect of 4 bicyclo[2.1.1]hexeno units fused to its 8-membered ring, are reported and interpreted. The perimeter model is applied to obtain an understanding of the nature of electronic states in 1 and 2 and to predict general trends in the spectra. The electronic excitation patterns are found to be different in the antiaromatic D-8h and unaromatic D-4h species, and their states cannot be unequivocally correlated. The results of time-dependent density functional theory and extended multistate complete active space second-order perturbation theory (XMS-CASPT2) computations agree with the algebraic perimeter model analysis and reproduce the spectra of 2 well, including three of the four observed MCD signs of A and B terms.

Název v anglickém jazyce

Magnetic circular dichroism of an unaromatic planar [8]annulene

Popis výsledku anglicky

An overview of magnetic circular dichroism (MCD) spectroscopy of pi-electron systems derived from a 4N-electron perimeter is provided, with emphasis on the hypothetical parent cycloocta-1,3,5,7-tetraene of D-8h symmetry (1) and its D-4h symmetry derivatives. UV-visible absorption and MCD spectra of 2, D-4h, symmetric cycloocta-1,3,5,7-tetraene planarized by the effect of 4 bicyclo[2.1.1]hexeno units fused to its 8-membered ring, are reported and interpreted. The perimeter model is applied to obtain an understanding of the nature of electronic states in 1 and 2 and to predict general trends in the spectra. The electronic excitation patterns are found to be different in the antiaromatic D-8h and unaromatic D-4h species, and their states cannot be unequivocally correlated. The results of time-dependent density functional theory and extended multistate complete active space second-order perturbation theory (XMS-CASPT2) computations agree with the algebraic perimeter model analysis and reproduce the spectra of 2 well, including three of the four observed MCD signs of A and B terms.

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

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Organic Chemistry

ISSN

0894-3230

e-ISSN

—

Svazek periodika

31

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

16

Strana od-do

—

Kód UT WoS článku

000441133000012

EID výsledku v databázi Scopus

2-s2.0-85047746279