Počet záznamů: 1
Detection of Indistinct Fe-N Stretching Bands in Iron(V) Nitrides by Photodissociation Spectroscopy
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SYSNO ASEP 0485420 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Detection of Indistinct Fe-N Stretching Bands in Iron(V) Nitrides by Photodissociation Spectroscopy Tvůrce(i) Andris, E. (CZ)
Navrátil, R. (CZ)
Jašík, J. (CZ)
Sabenya, G. (ES)
Costas, M. (ES)
Srnec, Martin (UFCH-W) RID, ORCID
Roithová, J. (CZ)Zdroj.dok. Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 24, č. 20 (2018), s. 5078-5081Poč.str. 4 s. Jazyk dok. eng - angličtina Země vyd. DE - Německo Klíč. slova photodissociation spectrochemistry ; infrared spectra ; DFT Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GJ15-10279Y GA ČR - Grantová agentura ČR Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000429703700015 EID SCOPUS 85040589690 DOI 10.1002/chem.201705307 Anotace We report for the first time infrared spectra of three non-heme pseudo-octahedral iron(V) nitride complexes with assigned Fe-N stretching vibrations. The intensities of the Fe-N bands in two of the complexes are extremely weak. Their detection was enabled by the high resolution and sensitivity of the experiments performed at 3K for isolated complexes in the gas phase. Multireference CASPT2 calculations revealed that the Fe-N bond in the ground doublet state is influenced by two low-lying excited doublet states. In particular, configuration interaction between the ground and the second excited state leads to avoided crossing of their potential energy surfaces along the Fe-N coordinate, which thus affects the ground-state Fe-N stretching frequency and intensity. Therefore, DFT calculated Fe-N stretching frequency strongly depends on the amount of Hartree-Fock exchange potential. As a result, by tuning the amount of Hartree-Fock exchange potential in the B3LYP functional, it was possible to obtain theoretical spectra perfectly consistent with the experimental data. The theory shows that the intensity of the Fe-N stretching vibration can almost vanish due to strong coupling with other stretching modes of the ligands. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2019
Počet záznamů: 1