On the Spectroscopic Modeling of Localized Defects in Sodalites by TD-DFT

Abstract

In this work, we designed a simulation protocol to investigate the spectroscopic properties of point defects in sodalite minerals, Na 8 Si 6 Al 6 O 24 Cl 2 , using time-dependent density functional theory. The F-center absorption spectrum and the sulfur impurity's (S 2 − ) fluorescence spectrum were simulated by considering different electrostatic environments around the cluster (embedded cluster model, ECM approach) and by coupling the electronic transition with vibrations obtained at the periodic boundary condition (PBC) level. These results highlight the influence of vibronic coupling in these spectra and of the confinement in the case of S 2 − fluorescence. The performances of 17 density functionals were assessed for the calculation of vertical excitation and emission energies against experimental values; global hybrids and generalized gradient approximation (GGA) gave the best results. The impact of chemical composition on the absorption spectra of the F-center was investigated, allowing the simulation of colors in absorption for 12 materials from the sodalite family.

Unravelling the Origin of the Yellow-Orange Luminescence in Natural and Synthetic Scapolites

“…During the submission process, authors learnt that a paper dedicated to the hackmanite material (not the scapolite) lead to similar results, although they were performed with other approximations. Authors are very thankful to referees for their valuable comments during the submission, in particular the third reviewer for computational suggestions.…”

Detection of X‐Ray Doses with Color‐Changing Hackmanites: Mechanism and Application

“…This cluster contains the sulfur impurity, the Na 4 tetrahedron and the β‐cage surrounding it. Following the previous work, [ 48 ] the cage was surrounded by a shell of cations described by pseudopotentials without the related basis set and a cloud of point charges. Point charges used to simulate the Madelung potential of the crystal were obtained through the Ewald package.…”

Structural Compactness in Hen Egg White Lysozyme Induced by Bisphenol S: A Spectroscopic and Molecular Dynamics Simulation Approach

“…The minimum energy docked conformation of Lyz‐BPS system was then analyzed using PyMOL software [48] to find the most probable locale of BPS within Lyz matrix. We further computed Time Dependent Density Functional Theory (TD‐DFT) quantum mechanical calculations for analyzing the energy gaps between Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) of tryptophan and BPS using Gaussian 09 software [46,49] . We also had employed the effects of solvents (water and MeOH) using the Polarizable Continuum Model (PCM) and the Integral Equation Formalism variant (IEFPCM) solvation model [50] …”