A Molecular Dynamics Study of Classical Vibrational Spectra in Hydrostatically Compressed Crystalline Nitromethane


The effects of pressure on the vibrational spectra of crystalline nitromethane have been studied by computing normal-mode frequencies and eigenvectors and classical power spectra at several hydrostatic pressures between 0 and 27.3 GPa using the full-dimensional Sorescu-Rice-Thompson (J. Phys. Chem. B 2000, 104, 8406) (SRT) valence force field. The purpose of the study was to determine the limits within which the SRT force field, and classical mechanics more generally, captures the qualitative pressure effects observed experimentally. The current results exhibit good overall agreement between the calculated normal-mode frequencies (and especially their pressure-dependent shifts) and those obtained in published experimental and theoretical studies. Comparisons of the pressure dependencies near room temperature of classical power spectra to experimental pressure-dependent infrared (IR) spectra for particular vibrational modes yield, in the case of the CN stretch, a CH3 deformation, and the NO2 asymmetric stretch, intriguingly similar evolution of spectral intensity with respect to pressure, whereas for the case of the NO2 symmetric stretch mode the classical result bears little similarity to the experimental result.



Keywords and Phrases

Computational chemistry; Crystalline materials; Hydrostatic pressure; Nitrogen oxides; Power spectrum; Pressure effects; Vibrational spectra, Classical mechanics; Force fields; Near room temperature; Nitromethane; Normal-mode frequencies; Power-spectra; Pressure dependencies; Spectral intensity; Theoretical study; Valence force fields; Vibrational modes, Molecular dynamics

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version


File Type





© 2010 American Chemical Society (ACS), All rights reserved.