摘要： Gas chromatography/mass spectrometry (GC/MS) is a "workhorse" instrument for chemical analysis, but it can be limited in its ability to differentiate structurally similar compounds. The coupling of GC to vacuum ultraviolet (VUV) spectroscopy is a recently developed technique with the potential for increased detection specificity. To date, GC/VUV has been demonstrated in the analysis of volatile organic compounds, petroleum products, aroma compounds, pharmaceuticals, illegal drugs, and lipids. This paper is the first to report on the utility of GC/VUV for explosives analysis in general, and the first to report on thermal degradation within the VUV cell and its analytical utility. The general figures of merit and performance of GC/VUV were evaluated with authentic standards of nitrate ester explosives (e.g., nitroglycerine (NG), ethylene glycol dinitrate (EGDN), pentaerythritol tetranitrate (PETN), and erythritol tetranitrate (ETN)). In addition, the explosive analytes were thermally degraded in the VUV cell, yielding reproducible, complex and characteristic mixtures of gas phase products (e.g., nitric oxide, carbon monoxide, and formaldehyde). The relative amounts of the degradation products were estimated via spectral subtraction of library spectra. Lastly, GC/VUV was used to analyze milligram quantities of intact and burned samples of double-base smokeless powders containing nitroglycerine, diphenylamine, ethyl centralite, and dibutylphthalate.