Spectroscopic signatures of states in the continuum characterized by a joint experimental and theoretical study of pyrrole

0566043 - ÚFCH JH 2023 RIV US eng J - Journal Article
Mukherjee, M. - Kumar, Ragesh Thelakkadan Puthiyaveettil - Ranković, Miloš - Nag, Pamir - Fedor, Juraj - Krylov, A. I.
Spectroscopic signatures of states in the continuum characterized by a joint experimental and theoretical study of pyrrole.
Journal of Chemical Physics. Roč. 157, č. 20 (2022), č. článku 204305. ISSN 0021-9606. E-ISSN 1089-7690
R&D Projects: GA ČR(CZ) GX21-26601X; GA MŠMT(CZ) LTAUSA19031
Institutional support: RVO:61388955
Keywords : Aromatic compounds * Electron energy levels * Energy dissipation
OECD category: Physical chemistry
Impact factor: 4.4, year: 2022
Method of publishing: Limited access

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.
Permanent Link: https://hdl.handle.net/11104/0337481