Solid-state modeling of the terahertz spectrum of the high explosive HMX

Damian G. Allis, Darya A. Prokhorova, Timothy M. Korter

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175 Scopus citations


The experimental solid-state terahertz (THz) spectrum (3-120 cm -1) of the β-crystal form of the high explosive octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX) has been analyzed using solid-state density functional theory calculations. Various density functionals (both generalized gradient approximation and local density approximation) are compared in terms of their abilities to reproduce the experimentally observed solid-state structure and low-frequency vibrational motions. Good-to-excellent agreement between solid-state theory and experiment can be achieved in the THz region where isolated-molecule calculations fail to reproduce the observed spectral features, demonstrating a clear limitation of using isolated-molecule calculations for the assignment of THz frequency motions in molecular solids. The deficiency of isolated-molecule calculations is traced to modification of the molecular structure in the solid state through crystal packing effects and the formation of weak C-H⋯O hydrogen bonds.

Original languageEnglish (US)
Pages (from-to)1951-1959
Number of pages9
JournalJournal of Physical Chemistry A
Issue number5
StatePublished - Feb 9 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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