The correlation between structure of chiral molecules and macroscopic prope
rties of cholesteric phases is not obvious, but often the experimental beha
viour can be rationalised by resorting to simple rules. However, there are
cases in which solvent / temperature changes or introduction of substituent
s in the chiral molecules can produce dramatic and unexpected effects, incl
uding helix inversion. Some significant examples will be presented and disc
ussed on the basis of theoretical predictions derived by the 'surface tenso
r' mean field model for molecular structures optimised with quantum-mechani
cal methods.