Experimental and Theoretical IR Spectra of 2-Nitrosopyridines
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00552733" target="_blank" >RIV/61388963:_____/20:00552733 - isvavai.cz</a>
Výsledek na webu
<a href="https://doi.org/10.5562/cca3820" target="_blank" >https://doi.org/10.5562/cca3820</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.5562/cca3820" target="_blank" >10.5562/cca3820</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Experimental and Theoretical IR Spectra of 2-Nitrosopyridines
Popis výsledku v původním jazyce
Previously unknown IR spectra of 2-nitrosopyridines 1−3 were recorded in the solid phase after cryogenic photolysis of their dimers, and identified by the comparison with the corresponding theoretical spectra. Optimal results were obtained with double-hybrid (DH) density functionals and def2-TZVP basis set, the best being DSD-PBEP86-D3(BJ), B2GP-PLYP-D3(BJ) and mPW2-PLYP-D2. Experimental frequencies were obtained by scaling harmonic frequencies with appropriate scaling factors, either taken from the literature or calculated using modified HFREQ2014 dataset. In the case of DH functionals, anharmonic frequencies do not offer any advantage in comparison with the scaled harmonic ones. Unexpectedly, all non-DH density functionals, including highly praised ωB97X-V and ωB97M-V, have serious problems with normal modes containing N=O bond stretching vibration. It was concluded that the origin of the problem is in the nitroso group itself, most likely caused by its multireference character. The best results among non-DH functionals were achieved at TPSSh-D3(BJ)/def2-TZVP level of theory.
Název v anglickém jazyce
Experimental and Theoretical IR Spectra of 2-Nitrosopyridines
Popis výsledku anglicky
Previously unknown IR spectra of 2-nitrosopyridines 1−3 were recorded in the solid phase after cryogenic photolysis of their dimers, and identified by the comparison with the corresponding theoretical spectra. Optimal results were obtained with double-hybrid (DH) density functionals and def2-TZVP basis set, the best being DSD-PBEP86-D3(BJ), B2GP-PLYP-D3(BJ) and mPW2-PLYP-D2. Experimental frequencies were obtained by scaling harmonic frequencies with appropriate scaling factors, either taken from the literature or calculated using modified HFREQ2014 dataset. In the case of DH functionals, anharmonic frequencies do not offer any advantage in comparison with the scaled harmonic ones. Unexpectedly, all non-DH density functionals, including highly praised ωB97X-V and ωB97M-V, have serious problems with normal modes containing N=O bond stretching vibration. It was concluded that the origin of the problem is in the nitroso group itself, most likely caused by its multireference character. The best results among non-DH functionals were achieved at TPSSh-D3(BJ)/def2-TZVP level of theory.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10401 - Organic chemistry
Návaznosti výsledku
Projekt
—
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2020
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Croatica Chemica Acta
ISSN
0011-1643
e-ISSN
1334-417X
Svazek periodika
93
Číslo periodika v rámci svazku
4
Stát vydavatele periodika
HR - Chorvatská republika
Počet stran výsledku
9
Strana od-do
339-347
Kód UT WoS článku
000751672900012
EID výsledku v databázi Scopus
2-s2.0-85123114191