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We explore the single-band envelope-function model in the entire Brillouin zone for electronic structure calculation of nanostructures that involve semiconductors with one or more significant valleys in the conduction band. Comparison with the numerically more demanding empirical pseudopotential calculation shows reasonably good accuracy of the method described here, which correctly predicts the quantized state energies, splittings in multivalley semiconductor nanostructures, as well as the intersubband transition derived optical properties. This makes it potentially useful for modeling nanostructures and nanodevices based on Si and other materials. © 2002 American Institute of Physics.