Validation of density functional methods for computing structures and energies of mercury(iv) complexes
文献信息
Sebastian Riedel, Michal Straka, Martin Kaupp
While quantum chemical predictions have strongly suggested a decade ago the existence of mercury in its oxidation state +IV, no experimental evidence has been found yet. To enable the search for alternative targets and preparation routes by quantum chemical methods, the present work has validated density functional methods against accurate CCSD(T) results for structures, reaction energies and activation barriers for X2-elimination, and atomization energies for three HgX4 systems (X = F, Cl, H). Hybrid functionals with ca. 20% Hartree–Fock exchange like B3LYP, B1LYP or MPW1PW91 have provided the best energetics, whereas local or gradient-corrected “pure” functionals overestimate, and the BHandHLYP hybrid functional underestimates the stability of the HgIV state. Basis sets are suggested that provide a reasonable compromise between accuracy and computational effort in calculations on larger systems.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.



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