Multireference theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: can we image molecular orbitals?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00638834" target="_blank" >RIV/61388955:_____/25:00638834 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/68378271:_____/25:00638834 RIV/61989592:15640/25:73631350

Výsledek na webu

<a href="https://hdl.handle.net/11104/0369404" target="_blank" >https://hdl.handle.net/11104/0369404</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.5c08166" target="_blank" >10.1021/jacs.5c08166</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Multireference theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: can we image molecular orbitals?

Popis výsledku v původním jazyce

Recent progress in on-surface chemistry has enabled the synthesis of novel polyradical molecules with interesting electronic structure, which are hardly available in solution chemistry. Moreover, the possibility to characterize their electronic structure with scanning tunneling spectroscopy (STS) with the unprecedented spatial resolution opens new possibilities to understand their nontrivial electronic structure. However, experimental STS maps of molecules on surfaces are interpreted using one-electron STM theory within the framework of one-electron molecular orbitals nowadays. Although this standard practice often gives relatively good agreement with experimental data for closed-shell molecules, it fails to address multireference polyradical molecules. In this manuscript, we provide multireference STM theory including out-of-equilibrium processes of removing/adding an electron within the formalism of many-electron wave functions for the neutral and charged states. This can be accomplished by the concept of so-called Dyson orbitals. We will discuss the examples where the concept of Dyson orbitals is mandatory to reproduce experimental STS maps of polyradical molecules. Finally, we critically review the possibility of the experimental verification of the so-called SOMO/HOMO inversion effect using STS maps in polyradical molecules. Namely, we will demonstrate that experimental STS measurements cannot provide any information in case of strongly correlated molecules about the ordering of one-electron molecular orbitals and, therefore neither about the SOMO/HOMO inversion effect.

Název v anglickém jazyce

Multireference theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: can we image molecular orbitals?

Popis výsledku anglicky

Recent progress in on-surface chemistry has enabled the synthesis of novel polyradical molecules with interesting electronic structure, which are hardly available in solution chemistry. Moreover, the possibility to characterize their electronic structure with scanning tunneling spectroscopy (STS) with the unprecedented spatial resolution opens new possibilities to understand their nontrivial electronic structure. However, experimental STS maps of molecules on surfaces are interpreted using one-electron STM theory within the framework of one-electron molecular orbitals nowadays. Although this standard practice often gives relatively good agreement with experimental data for closed-shell molecules, it fails to address multireference polyradical molecules. In this manuscript, we provide multireference STM theory including out-of-equilibrium processes of removing/adding an electron within the formalism of many-electron wave functions for the neutral and charged states. This can be accomplished by the concept of so-called Dyson orbitals. We will discuss the examples where the concept of Dyson orbitals is mandatory to reproduce experimental STS maps of polyradical molecules. Finally, we critically review the possibility of the experimental verification of the so-called SOMO/HOMO inversion effect using STS maps in polyradical molecules. Namely, we will demonstrate that experimental STS measurements cannot provide any information in case of strongly correlated molecules about the ordering of one-electron molecular orbitals and, therefore neither about the SOMO/HOMO inversion effect.

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

2025

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

147

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

24993-25003

Kód UT WoS článku

001521553300001

EID výsledku v databázi Scopus

2-s2.0-105009603474