This is a property of the font. Every character of the font has four associated lengths specified in the tfm (font metric) file. Height, Width, Depth and Italic Correction.
When you use \/ TeX extracts the dimension from the font metric file, scales it by any scaling that has been applied to the font and then inserts that much horizontal space.
Often you need aesthetic judgement around punctuation as to whether it is needed. (But LaTeX \textrm and similar command do apply it automatically and get it mostly right.)
Well the correction spacing is applied, and also any ligatures or kerns that would be between those letters are lost. (Originally I added most of the time here).
{}to break ligatures, that does fail after hyphenation and\/is a suggested fix TeX(3) book says In fact, the latter idea-to insert an italic correction-is preferable because TeX will reinsert the ff ligature by itself after hyphenatingshelf{}ful(Appendix~H points out that ligatures are put into a hyphenated word that contains no explicit kerns,and an italic correction is an explicit kern.) But the italic correction may be too much (especially in anitalic font); shelf{\kern0pt}ful is often best. – David Carlisle Jan 15 '13 at 21:44\/(like\/\/\/\/) seems to have the same effect as applying just one\/. – Lover of Structure Jan 17 '13 at 11:15\/looks at the previous item (in the list being typeset) and if that is a character it looks up the italic correction, for a second\/the previous item will be a kern from the first one, so later ones don't see a character and so do nothing. – David Carlisle Jan 17 '13 at 11:25shelf{}ful", which I'm not quite following. – Lover of Structure Jan 19 '13 at 00:06