Guevara-Vela José Manuel, Gallegos Miguel, Rocha-Rinza Tomás, Muñoz-Castro Álvaro, Kessler Peter L Rodríguez, Martín Pendás Ángel
Departamento de Química Física Aplicada, Universidad Autónoma de Madrid, C. Francisco Tomás y Valiente, 7, Madrid, 28049, Spain.
Departamento de Química Física y Analítica, Universidad de Oviedo, Av. Julián Clavería, 8, Oviedo, 33006, Asturias, Spain.
J Mol Model. 2024 Aug 17;30(9):310. doi: 10.1007/s00894-024-06099-5.
The study of platinum (Pt) clusters and nanoparticles is essential due to their extensive range of potential technological applications, particularly in catalysis. The electronic properties that yield optimal catalytic performance at the nanoscale are significantly influenced by the size and structure of Pt clusters. This research aimed to identify the lowest-energy conformers for Pt , Pt , and Pt species using Density Functional Theory (DFT). We discovered new low-symmetry conformers for Pt and Pt , which are 3.0 and 1.0 kcal/mol more stable, respectively, than previously reported structures. Our study highlights the importance of using density functional approximations that incorporate moderate levels of exact Hartree-Fock exchange, alongside basis sets of at least quadruple-zeta quality. The resulting structures are asymmetric with varying active sites, as evidenced by sigma hole analysis on the electrostatic potential surface. This suggests a potential correlation between electronic structure and catalytic properties, warranting further investigation.
An equivariant graph neural network interatomic potential (NequIP) within the Atomic Simulation Environment suite (ASE) was used to provide initial geometries of the aggregates under study. DFT calculations were performed with the ORCA 5 package, using functional approximations that included Generalized Gradient Approximation (PBE), meta-GGA (TPSS, M06-L), hybrid (PBE0, PBEh), meta-GGA hybrid (TPSSh), and range-separated hybrid ( B97x) functionals. Def2-TZVP and Def2-QZVP as well as members of the cc-pwCVXZ-PP family to check basis set convergence were used. QTAIM calculations were performed using the AIMAll suite. Structures were visualized with the AVOGADRO code.
由于铂（Pt）团簇和纳米颗粒具有广泛的潜在技术应用，特别是在催化领域，因此对它们的研究至关重要。在纳米尺度上产生最佳催化性能的电子性质受到Pt团簇的大小和结构的显著影响。本研究旨在使用密度泛函理论（DFT）确定Pt₂、Pt₃和Pt₄物种的最低能量构象。我们发现了Pt₂和Pt₃的新的低对称构象，它们分别比先前报道的结构稳定3.0和1.0千卡/摩尔。我们的研究强调了使用包含适度精确Hartree-Fock交换水平的密度泛函近似以及至少四重zeta质量的基组的重要性。如对静电势表面的sigma空穴分析所示，所得结构是不对称的，具有不同的活性位点。这表明电子结构与催化性能之间可能存在相关性，值得进一步研究。
使用原子模拟环境套件（ASE）中的等变图神经网络原子间势（NequIP）来提供所研究聚集体的初始几何结构。使用ORCA 5软件包进行DFT计算，使用的泛函近似包括广义梯度近似（PBE）、meta-GGA（TPSS、M06-L）、杂化（PBE0、PBEh）、meta-GGA杂化（TPSSh）和范围分离杂化（B97x）泛函。使用Def2-TZVP和Def2-QZVP以及cc-pwCVXZ-PP族的成员来检查基组收敛性。使用AIMAll套件进行QTAIM计算。使用AVOGADRO代码对结构进行可视化。
