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

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00566043" target="_blank" >RIV/61388955:_____/22:00566043 - isvavai.cz</a>

Result on the web

<a href="https://hdl.handle.net/11104/0337481" target="_blank" >https://hdl.handle.net/11104/0337481</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0123603" target="_blank" >10.1063/5.0123603</a>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2022

Confidentiality

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

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Volume of the periodical

157

Issue of the periodical within the volume

20

Country of publishing house

US - UNITED STATES

Number of pages

15

Pages from-to

204305

UT code for WoS article

000910984700013

EID of the result in the Scopus database

2-s2.0-85143182818