Issue 41, 2021

Fe(phen)2(NCS)2 on Al(100): influence of AlN layer on spin crossover barrier

Abstract

We study how a nitride layer affects spin crossover (SCO) in a single Fe(phen)2(NCS)2 (Fephen) molecule adsorbed on the Al(100) surface using ab initio calculations. The Coulomb correlation of the open-shell 3d electrons has been considered using a Hubbard-U correction within different exchange–correlation approximations, including the van der Waals density functional. We determine the SCO energy barrier by computing the minimum energy path between the high-spin (HS) and low-spin (LS) states via direct constraint relaxations. It is shown that the HS–LS energy difference is slightly increased once deposited on Al(100), and thus LS states tend to be stabilized, as usually observed on metallic substrates. The oxidation of metallic Al to aluminum ions in the AlN layer promotes molecular adsorption, while it decreases HS–LS splitting, making Fephen switchable between its two spin states. Due to enhanced molecule–substrate bonding, the SCO barrier height is considerably increased, which may promote cooperativity. This effect is consistent with the AlN facilitated charge transfer at the interface that results from a reduction in surface work function. Our findings reveal the crucial role that surface electronic structure plays in maintaining spin bistability of the molecular adsorbate.

Graphical abstract: Fe(phen)2(NCS)2 on Al(100): influence of AlN layer on spin crossover barrier

Article information

Article type
Paper
Submitted
17 Aug 2021
Accepted
27 Sep 2021
First published
28 Sep 2021

Phys. Chem. Chem. Phys., 2021,23, 23758-23767

Fe(phen)2(NCS)2 on Al(100): influence of AlN layer on spin crossover barrier

Y. Zhang, Phys. Chem. Chem. Phys., 2021, 23, 23758 DOI: 10.1039/D1CP03782J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements