Investigating anharmonicity using molecular dynamics calculations: The TM hydride series (PH3)3MH4, (M = Os, Ru and Fe)

Carole A. Morrison, Anthony M. Reilly

Research output: Contribution to journalArticlepeer-review


We present an ab initio molecular dynamics study of the iron triad complex (PH3)3MH4, (M = Os, Ru and Fe). We calculate numerical atomic probability density functions (PDFs), which offer direct visualisation of the degree of anharmonicity present in these complexes. Fitting our calculated PDFs to a parabolic transformation of the standard crystallographic ellipsoidal PDF allowed the bond correction for librational motion observed in the M-H distances to be obtained. For the Ru and Fe complexes we also attempt to quantify the bond distance correction needed to describe the η2-bound H2 ligand anharmonically. From our simulations we also obtain anharmonic vibrational spectra, which we compare to experimental data. Finally, we also comment on a spontaneous H2/(H)2 ligand flipping process observed for the Fe complex.

Original languageEnglish
Pages (from-to)5527-5534
Number of pages8
JournalDalton Transactions
Issue number23
Publication statusPublished - 21 Jun 2010

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