This paper, the fifth in a series, is concerned with the experimental description of ultrafast electron diffraction
and its application to several isolated chemical systems. We present a detailed description of the Caltech apparatus, which consists of a femtosecond laser system, a picosecond electron gun, and a two-dimensional charge-coupled device ( CCD) detection system. We also discuss the analysis of the scattering patterns. Ultrafast diffraction images from several molecules (CCl_4, I_2, CF_3l, C_2F_4I_2) are reported. For our first study of a chemical reaction in a molecular beam, we show the change in the radial distribution function following the formation of CF_3 radical after dissociation of CF_3l. The total experimental temporal resolution is discussed in terms of the electron pulse width and velocity mismatch. The electron pulse was characterized temporally with a streaking technique that yielded the width as a function of the number of electrons per pulse. Experimental results show that the electron source produces picosecond (or less) pulses at densities of 100 electrons per pulse and 10-ps pulses at 1000 electrons per pulse. We also report our observation of a novel photoionization-induced lensing effect on the undiffracted electron beam, which we have used to establish time zero for UED when reactions are initiated by a laser pulse.