Interpretation of Exchange Interaction through Orbital Entanglement

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F21%3A00540524" target="_blank" >RIV/61388963:_____/21:00540524 - isvavai.cz</a>

Alternative codes found

RIV/61388955:_____/21:00540524

Result on the web

<a href="https://doi.org/10.1021/acs.jpclett.0c03652" target="_blank" >https://doi.org/10.1021/acs.jpclett.0c03652</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.0c03652" target="_blank" >10.1021/acs.jpclett.0c03652</a>

Result language

angličtina

Original language name

Interpretation of Exchange Interaction through Orbital Entanglement

Original language description

Recently, the analysis of single-orbital entropy and mutual information has been introduced as a tool for the investigation of contributions to the exchange (J) coupling between open-shell metal ions [Stein et al. J. Phys. Chem. Lett. 2019, 10, 6762-6770]. Here, we show that this analysis may lead to an incorrect interpretation of the J-coupling mechanism. Instead, we propose an orbital-entanglement analysis that is based on the two-electron density and that provides a coherent picture of the contributing exchange pathways, which seems fully consistent with the available J values. For this purpose, we used a prototypical bis-μ-oxo binuclear manganese complex ([Mn2O2(NH3)8]4+) and demonstrated that its antiferromagnetism (J < 0), calculated by using the active space composed of all valence pO and dMn orbitals, correlates well with the largest elements in the differential low-spin vs high-spin entanglement map. These elements correspond to interactions between the pairs of dMn orbitals mediated by the oxo-bridging out-of-plane p orbitals, representing the πsuperexchange pathway. We also show that the reduction of active space to manifold of the singly occupied magnetic orbitals does not lead to discrepancy between the calculated J values and entanglement maps. This contrasts to analysis of mutual information, which suggests the 'direct'dMn-dMn interactions to play a dominant role for the J coupling, irrespective of the size of active space as well as of the antiferromagnetism expected. The failure is attributed to the large contribution of spin entanglement contained in the mutual information of the low-spin state, which may be regarded as the origin of the different complexity of its wave function and electron density.

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

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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

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2021

Confidentiality

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

Name of the periodical

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Volume of the periodical

12

Issue of the periodical within the volume

4

Country of publishing house

US - UNITED STATES

Number of pages

7

Pages from-to

1268-1274

UT code for WoS article

000618526700025

EID of the result in the Scopus database

2-s2.0-85100710037