Lattice Structure and Dynamics of Sparse Molecular Crystals: OsO4 and RuO4

Raghuvanshi, Parul R.; Wang, Shaofei; Phillips, Jana; Abernathy, Douglas; Daemen, Luke; Cooper, Valentino R.; Lindsay, Lucas; Hermann, Raphael P.; Parker, David S.

doi:10.1021/acs.jpcc.4c08816

Lattice Structure and Dynamics of Sparse Molecular Crystals: OsO₄ and RuO₄

Journal Article · Tue Apr 08 00:00:00 EDT 2025 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.4c08816· OSTI ID:2573423

^[1]; ^[1]; Phillips, Jana ^[1]; Abernathy, Douglas ^[1]; Daemen, Luke ^[1]; ^[1]; Lindsay, Lucas ^[1]; ^[1]; Parker, David S. ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

OsO₄ and RuO₄ are molecular oxides with unique tetrameric structures and rare +8 oxidation states. Accurately modeling their properties remains challenging for density functional theory (DFT) due to weak intertetramer interactions, which standard functionals fail to capture. Here, in this work, we show that the van der Waals (vdW)-corrected density functional (vdW-DF-optB86b) provides structural parameters that are much closer to experimental values than the standard generalized gradient approximation, with volume predictions that fall within the experimentally observed range. Phonon band structure analysis shows that the inclusion of vdW interactions stabilizes soft phonon modes, highlighting the importance of dispersion corrections for accurate predictions of lattice dynamics. Experimental measurements of the phonon density of states for OsO₄, obtained via inelastic neutron scattering, demonstrate good agreement with our vdW-DF-optB86b calculations. These results validate OsO₄ and RuO₄ as valuable benchmarks for structural and vibrational calculations via vdW-corrected DFT methods and offer insights for studying the broader class of sparse molecular materials.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2573423

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 15 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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