Electronic structure of the solvated benzene radical anion

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00552869" target="_blank" >RIV/61388963:_____/22:00552869 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11320/22:10439528

Výsledek na webu

<a href="https://doi.org/10.1063/5.0076115" target="_blank" >https://doi.org/10.1063/5.0076115</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0076115" target="_blank" >10.1063/5.0076115</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electronic structure of the solvated benzene radical anion

Popis výsledku v původním jazyce

The benzene radical anion is a molecular ion pertinent to several organic reactions, including the Birch reduction of benzene in liquid ammonia. The species exhibits a dynamic Jahn–Teller effect due to its open-shell nature and undergoes pseudorotation of its geometry. Here, we characterize the complex electronic structure of this condensed-phase system based on ab initio molecular dynamics simulations and GW calculations of the benzene radical anion solvated in liquid ammonia. Using detailed analysis of the molecular and electronic structure, we find that the spatial character of the excess electron of the solvated radical anion follows the underlying Jahn–Teller distortions of the molecular geometry. We decompose the electronic density of states to isolate the contribution of the solute and to examine the response of the solvent to its presence. Our findings show the correspondence between instantaneous molecular structure and spin density, provide important insights into the electronic stability of the species, revealing that it is, indeed, a bound state in the condensed phase, and offer electronic densities of states that aid in the interpretation of experimental photoelectron spectra.

Název v anglickém jazyce

Electronic structure of the solvated benzene radical anion

Popis výsledku anglicky

The benzene radical anion is a molecular ion pertinent to several organic reactions, including the Birch reduction of benzene in liquid ammonia. The species exhibits a dynamic Jahn–Teller effect due to its open-shell nature and undergoes pseudorotation of its geometry. Here, we characterize the complex electronic structure of this condensed-phase system based on ab initio molecular dynamics simulations and GW calculations of the benzene radical anion solvated in liquid ammonia. Using detailed analysis of the molecular and electronic structure, we find that the spatial character of the excess electron of the solvated radical anion follows the underlying Jahn–Teller distortions of the molecular geometry. We decompose the electronic density of states to isolate the contribution of the solute and to examine the response of the solvent to its presence. Our findings show the correspondence between instantaneous molecular structure and spin density, provide important insights into the electronic stability of the species, revealing that it is, indeed, a bound state in the condensed phase, and offer electronic densities of states that aid in the interpretation of experimental photoelectron spectra.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

156

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

014501

Kód UT WoS článku

000745647600005

EID výsledku v databázi Scopus

2-s2.0-85122310403