Počet záznamů: 1
Spectroscopic signatures of states in the continuum characterized by a joint experimental and theoretical study of pyrrole
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SYSNO ASEP 0566043 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Spectroscopic signatures of states in the continuum characterized by a joint experimental and theoretical study of pyrrole Tvůrce(i) Mukherjee, M. (US)
Kumar, Ragesh Thelakkadan Puthiyaveettil (UFCH-W) ORCID, RID
Ranković, Miloš (UFCH-W) ORCID, RID
Nag, Pamir (UFCH-W) ORCID, RID, SAI
Fedor, Juraj (UFCH-W) ORCID
Krylov, A. I. (US)Číslo článku 204305 Zdroj.dok. Journal of Chemical Physics. - : AIP Publishing - ISSN 0021-9606
Roč. 157, č. 20 (2022)Poč.str. 15 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova Aromatic compounds ; Electron energy levels ; Energy dissipation Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GX21-26601X GA ČR - Grantová agentura ČR LTAUSA19031 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Způsob publikování Omezený přístup Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000910984700013 EID SCOPUS 85143182818 DOI 10.1063/5.0123603 Anotace We report a combined experimental and theoretical investigation of electron-molecule interactions using pyrrole as a model system. Experimental two-dimensional electron energy loss spectra (EELS) encode information about the vibrational states of the molecule as well as the position and structure of electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features. We confirm the two previously described π resonances at about 2.5 and 3.5 eV (the calculations place these two states at 2.92 and 3.53 eV vertically and 2.63 and 3.27 eV adiabatically). The calculations also predict a low-lying resonance at 0.46 eV, which has a mixed character of a dipole-bound state and σ∗ type. This resonance becomes stabilized at one quanta of the NH excitation, giving rise to the sharp feature at 0.9 eV in the corresponding EELS. Calculations of Franck-Condon factors explain the observed variations in the vibrational excitation patterns. The ability of theory to describe EELS provides a concrete illustration of the utility of non-Hermitian quantum chemistry, which extends such important concepts as potential energy surfaces and molecular orbitals to states embedded in the continuum. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2023 Elektronická adresa https://hdl.handle.net/11104/0337481
Počet záznamů: 1