Arnaud Fihey | Searcharxiv

arXiv2026

Fast and accurate simulation of Raman spectra of gold-organic systems

Resolving the spectral Raman signature of molecules grafted on a metallic support is often a difficult task, in which quantum chemistry methods allow for precious additional rationalization and signal attributions, especially to probe the formation of a bond with the support. In the specific case of gold-organic architectures based on a Au-C bond, only a limited amount of experimental and theoretical reference data are available in the literature, and Raman simulations based on quantum mechanics quickly become unaffordable with the size of the system. In this work, we evaluate the precision of a cost-efficient DFTB method to simulate Raman spectra of gold-organic systems at different scales, from gold complexes to functionalized gold surfaces. After a validation of the method through a careful comparison of DFTB Raman spectra of organometallic gold(I) and (III) complexes to DFT and experimental reference data, we discuss the case of molecules grafted on gold aggregates. For these simulations, the choice of the model (cluster or periodic surface) appears to be critical, and significant differences arise (positions and intensities of the peaks) when considering a full metallic slab, as allowed by the low computational cost of the method.

physics.chem-ph↗

arXiv2024

Flexible and Efficient Semi-Empirical DFTB Parameters for Electronic Structure Prediction of 3D, 2D Iodide Perovskites and Heterostructures

Density Functional Tight-Binding (DFTB), an approximative approach derived from Density Functional Theory (DFT), has the potential to pave the way for simulations of large periodic or non-periodic systems. We have specifically tailored DFTB parameters to enhance the accuracy of electronic band gap calculations in both 3D and 2D lead-iodide perovskites, at a significantly reduced computational cost relative to state-of-the-art ab initio calculations. Our electronic DFTB parameters allow computing not only the band gap but also effective masses of perovskite materials with reasonable accuracy compared to existing experimental data and state-of-the-art DFT calculations. The electronic band structures of vacancy-ordered and, lead- and iodide- deficient perovskites are also explored. Additionally, we demonstrate the efficiency of DFTB in computing electronic band alignments in perovskite heterostructures. The DFTB-based approach is anticipated to be beneficial for studying large-scale systems such as heterostructures and nanocrystals.

cond-mat.mtrl-sci↗