Density functional benchmarks for methylaluminoxane: successes, biases, and transferability limits
Abstract
. ωB97X-D4 and MN15 show the largest errors and should be avoided for pure MAO systems. Two functionals, ωB97X-V and ωB97M-D4, accurately reproduce reference electronic energies without structural bias. For vibrational properties, quasi-harmonic treatment effectively reduces method-dependent entropy variations, and thermochemical corrections prove robust across functionals. However, extending these methods to metallocene-MAO ion pairs reveals distinct system-dependent behavior that warrants further investigation. Together, these findings highlight that functional performance is system-dependent, with significant implications for computational studies of catalyst activation mechanisms.
Fields of Study & Subjects
Organometallic Complex Synthesis and Catalysis
Advanced Polymer Synthesis and Characterization
Metal-Catalyzed Oxygenation Mechanisms
Publication details
- Journal / source
- Physical Chemistry Chemical Physics
- Publisher
- Royal Society of Chemistry (RSC)
- Volume
- 28
- Issue
- 30
- Pages
- 18478–18490
- Publication date
- 1 January 2026
- Language
- EN