TY - JOUR
T1 - Benchmarking Density Functional Theory for Noble Metal Hydrides: A High-Fidelity PES and Vibrational Analysis of the ${\rm AgAuH}^−$ Anion
AU - Feng , Yuquan
AU - Zhao , Kaiyi
AU - Chen , Jun
JO - Communications in Computational Chemistry
VL - 4
SP - 274
EP - 280
PY - 2025
DA - 2025/09
SN - 7
DO - http://doi.org/10.4208/cicc.2025.146.02
UR - https://global-sci.org/intro/article_detail/cicc/24348.html
KW - ${\rm AgAuH}^−,$ density functional theory benchmarking, high-level ab initio potential energy surface, vibrational quantum dynamics, coinage metal hydrides.
AB - <p style="text-align: justify;">The accurate description of noble metal hydrides remains a fundamental challenge for electronic structure theory, especially in systems involving heavy elements where relativistic effects and electron correlation are significant. In this study, we present a high-accuracy potential energy surface (PES) for the ${\rm AgAuH}^−$ anion, constructed from 3,595 UCCSD(T)-F12a
energy points and fitted using a feedforward neural network with a root mean square error of 0.21 meV. The PES captures the
entire configuration space, including linear and bent minima, transition-state-like structures, and dissociation pathways. Quantum vibrational bound states were computed using time-independent quantum dynamics, enabling detailed mode
assignments. The high-fidelity PES and vibrational dataset were used to benchmark some widely employed density functional
theory (DFT) methods, B3LYP, ωB97XD, XYG3, and XYGJ-OS. Among these, XYGJ-OS provided the best agreement with
the reference data in terms of equilibrium geometries and vibrational frequencies. This study provides a robust benchmark for method development and validation in metal-containing systems and highlights the importance of using high-level reference data when modeling complex coinage-metal hydrides.</p>