Abstract
For the first time a secondary ion mass spectrum of diethyl ether was obtained at low temperature. The spectrum recording became possible by carefully selecting the range of experimental conditions for the production of a cluster‐type spectrum. This range is specified by the threshold for spectrum appearance above the melting temperature of the frozen sample and a fairly short time span of existence of the liquid estimated as only a few minutes. The latter necessitates rather rapid spectrum detection. In practice, about 1 min was available for recording of the cluster‐type spectra. The secondary emission mass spectrum of diethyl ether appeared to be rich in peaks: along with abundant protonated clusters M~n~·H^+^ (n = 1–12), unusually intense [M~n~ − H]^+^ and weaker M~n~^+·^ peaks were present accompanied by several sets of fragmented clusters, [M~n~ − 15]^+^, [M~n~ − 29]^+^, [M~n~ − 27]^+^, [M~n~ − 45]^+^, and monohydrates, M~n~·H~2~O·H^+^. The analysis of all the peaks showed that the pattern of fragment clusters is qualitatively similar to the pattern of fragmentation of the diethyl ether molecular ion under high‐energy electron impact. The general features of the behaviour of diethyl ether under low‐temperature mass spectrometric conditions were similar to those observed earlier for some other organic solvents. Copyright © 2003 John Wiley & Sons, Ltd.