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

Result code in 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>

Alternative codes found

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

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

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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

2025

Confidentiality

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

Name of the periodical

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Volume of the periodical

147

Issue of the periodical within the volume

28

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

24993-25003

UT code for WoS article

001521553300001

EID of the result in the Scopus database

2-s2.0-105009603474