Modeling the polychromism of oxide minerals: The case of alexandrite and cordierite.

In this work, we investigate the spectroscopic properties of photochromic alexandrite and cordierite by TD-DFT. The objective is to assess the TD-DFT for the simulation of pleochroism (change of color depending on the crystallographic direction of the observation) and the change of color as a function of the light source. For these simulations, we compared an embedding where dangling bonds are saturated by hydrogen atoms and an electrostatic embedding. The electrostatic embedding provided numerically more stable results and allowed a good reproduction of the pleochroism of cordierite, based on a Fe2+-Fe3+ intervalence charge transfer transition. However, the pleochroism of alexandrite is not as well reproduced, suggesting that TD-DFT has some difficulties to reproduce the anisotropy of the transition dipole moment, an aspect that is not deeply documented in the literature.

Reusable radiochromic hackmanite with gamma exposure memory.

Radiochromic films are used as position-sensitive dose meters in e.g. medical physics and radiation processing. The currently available films like those based on lithium-10,12-pentacosdiynoate or leucomalachite green are either toxic or non-reusable, or both. There is thus a great need for a sustainable solution for radiochromic detection. In the present work, we present a suitable candidate: hackmanite with the general formula Na8Al6Si6O24(Cl,S)2. This material is known as a natural intelligent material capable of changing color when exposed to ultraviolet radiation or X-rays. Here, we show for the first time that hackmanites are also radiochromic when exposed to alpha particles, beta particles (positrons) or gamma radiation. Combining experimental and computational data we elucidate the mechanism of gamma-induced radiochromism in hackmanites. We show that hackmanites can be used for gamma dose mapping in high dose applications as well as a memory material that has the one-of-a-kind ability to remember earlier gamma exposure. In addition to satisfying the requirements of sustainability, hackmanites are non-toxic and the films made of hackmanite are reusable thus showing great potential to replace the currently available radiochromic films.

The structural origin of the efficient photochromism in natural minerals.

SignificanceNatural photochromic minerals have been reported by geologists for decades. However, the understanding of the photochromism mechanism has a key question still unanswered: What in their structure gives rise to the photochromism's reversibility? By combining experimental and computational methods specifically developed to investigate this photochromism, this work provides the answer to this fundamental question. The specific crystal structure of these minerals allows an unusual motion of the sodium atoms stabilizing the electronic states associated to the colored forms. With a complete understanding of the photochromism mechanism in hand, it is now possible to design new families of stable and tunable photochromic inorganic materials-based devices.

OPTIMADE, an API for exchanging materials data.

The Open Databases Integration for Materials Design (OPTIMADE) consortium has designed a universal application programming interface (API) to make materials databases accessible and interoperable. We outline the first stable release of the specification, v1.0, which is already supported by many leading databases and several software packages. We illustrate the advantages of the OPTIMADE API through worked examples on each of the public materials databases that support the full API specification.

Two-sites are better than one: revisiting the OER mechanism on CoOOH by DFT with electrode polarization.

We uncover the existence of several competitive mechanisms of water oxidation on the ß-CoOOH (10-14) surface by going beyond the classical 4-step mechanism frequently used to study this reaction at the DFT level. Our results demonstrate the importance of two-site reactivity and of purely chemical steps with the associated activation energies. Taking the electrochemical potential explicitly into account leads to modifications of the reaction energy profiles finally leading to the proposition of a new family of mechanisms involving tetraoxidane intermediates. The two-site mechanisms revealed in this work are of key importance to rationalize and predict the impact of dopants in the design of future catalysts.