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We study the structure of the energy spectra along with the character of thestates participating in optical transitions in colloidal CdS quantum dots (QDs)using the {\sl ab initio} accuracy charge patching method combined with the%pseudopotential based folded spectrum calculations of electronic structure ofthousand-atom nanostructures. In particular, attention is paid to the nature ofthe large resonant Stokes shift observed in CdS quantum dots. We find that thetop of the valence band state is bright, in contrast with the results ofnumerous {\bf k$\cdot$p} calculations, and determine the limits ofapplicability of the {\bf k$\cdot$p} approach. The calculated electron-holeexchange splitting suggests the spin-forbidden valence state may explain thenature of the ``dark exciton'' in CdS quantum dots.Comment: 5 pages, 4 figure

Optical transitions and nature of Stokes shift in spherical CdS quantum dots