Accurate Computation of Cohesive Energies for Small to Medium-Sized Gold Clusters

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• 作者：Bun Chan ; Wai-Leung Yim
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：April 9, 2013
• 年：2013
• 卷：9
• 期：4
• 页码：1964-1970
• 全文大小：242K
• 年卷期：v.9,no.4(April 9, 2013)
• ISSN：1549-9626

文摘

High-level CCSD(T)-F12-type procedures have been used to assess the performance of a variety of computationally less demanding methods for the calculation of cohesive energies for small to medium-sized gold clusters. For geometry optimization for small gold clusters, the PBE-PBE/cc-pVDZ-PP procedure gives structures that are in close agreement with the benchmark geometries. We have devised a CCSD(T)-F12b-based composite protocol for the accurate calculation of cohesive energies for medium-sized gold clusters. Using these benchmark (nonspin鈥搊rbit vibrationless) cohesive energies, we find that fairly good agreement is achieved by the PBE-PBE-D3/cc-pVTZ-PP method. In conjunction with PBE-PBE/cc-pVDZ-PP zero-point vibrational energies and spin-obit corrections obtained with the PBE-PBE-2c/dhf-TZVP-2c method, we have calculated 0 K cohesive energies for Au₂鈥揂u₂₀. Extrapolation of these cohesive energies to bulk yields an estimated value of 383.2 kJ mol^鈥?, which compares reasonably well with the experimental value of 368 kJ mol^鈥?.