Effects of Dispersion Corrections and Nonlocality on Density Functional Predictions of Pressure-Induced Polymorphic Transitions of Crystalline Diborane
| Autor: | Angela M. Murcia Rios, Viktor N. Staroverov, Darya N. Komsa |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Physics
010304 chemical physics Gaussian basis set Hydride Thermodynamics chemistry.chemical_element 01 natural sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Pressure range symbols.namesake Quantum nonlocality chemistry.chemical_compound General Energy chemistry 0103 physical sciences Physics::Atomic and Molecular Clusters symbols Chemical stability Physical and Theoretical Chemistry van der Waals force 010306 general physics Boron Diborane |
| Zdroj: | The Journal of Physical Chemistry C. 122:14781-14787 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.8b02431 |
| Popis: | The role of dispersion interactions in density functional calculations of the relative enthalpies of compressed BH3 polymorphs was investigated using plane-wave and Gaussian basis set codes. Addition of semiempirical atom-pairwise dispersion corrections to generalized gradient approximations (GGAs) was found to have little effect on the relative enthalpies of various boron hydride structures. By contrast, the stability ranking obtained with the nonlocal van der Waals density functional (vdW-DF) of Dion and co-workers was substantially more realistic than the rankings predicted by plain and dispersion-corrected GGAs. Of the functionals tested, only vdW-DF correctly predicts that compressed diborane does not leave the B2H6 motif until at least 20 GPa. This finding serves as direct computational evidence of the thermodynamic stability of molecular B2H6 units in the 0–20 GPa pressure range, an experimental result that until now has been at variance with theoretical predictions. |
| Databáze: | OpenAIRE |
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