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Peter,
The easiest way to make a start is to get a Star Analyser or Rainbow Optic grating. Either of these can be fitted into the nosepiece of your camera (webcam, CCD or DSLR)
Mounted on a scope they will quickly show you the spectra of the brighter stars.
Processing the spectra can be done with the freeware IRIS and VSpec or Tom Field's commercial package RSpec.
Com' on over - you'll love it!
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