Interpretation of Exchange Interaction through Orbital Entanglement

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/61388955:_____/21:00540524

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Interpretation of Exchange Interaction through Orbital Entanglement

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Interpretation of Exchange Interaction through Orbital Entanglement

Popis výsledku anglicky

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.

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

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

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

12

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

1268-1274

Kód UT WoS článku

000618526700025

EID výsledku v databázi Scopus

2-s2.0-85100710037