  We have combined large-scale, $\Gamma$-point electronic-structure
calculations with the maximally-localized Wannier functions approach to
calculate efficiently the band structure and the quantum conductance of complex
systems containing thousands of atoms while maintaining full first-principles
accuracy. We have applied this approach to study covalent functionalizations in
metallic single-walled carbon nanotubes. We find that the band structure around
the Fermi energy is much less dependent on the chemical nature of the ligands
than on the $sp^3$ functionalization pattern disrupting the conjugation
network. Common aryl functionalizations are more stable when paired with
saturating hydrogens; even when paired, they still act as strong scattering
centers that degrade the ballistic conductance of the nanotubes already at low
degrees of coverage.
