The mixing between
Γ and
X conduction band valleys in GaAs–
Ga1-xAlxAs quantum wells is investigated along the lines of a variational model. Trial wavefunctions are depending on a weighting variational parameter that accounts for the mixing by acting as a coefficient in the combination of both uncorrelated
Γ and
X states in the system. The dependencies of the calculated binding energy of a donor impurity and the correlated electron–hole photoluminescence peak energy upon hydrostatic pressure and quantum well width are presented.