We present radiative transfer simulations for blue kilonovae hours after neutron star (NS) mergers by performing detailed opacity calculations for the first time. We calculate atomic structures and opacities of highly ionized elements (up to the tenth ionization) with atomic number Z = 20 - 56. We find that the bound-bound transitions of heavy elements are the dominant source of the opacities in the early phase (t < 1 day after the merger), and that the ions with a half-closed electron shell provide the highest contributions. The Planck mean opacity for lanthanide-free ejecta (with electron fraction of Ye = 0.30 - 0.40) can only reach around kappa ~ 0.5 - 1 cm^2 g^-1 at t = 0.1 day, whereas that increases up to kappa ~ 5 - 10 cm^2 g^-1 at t = 1 day. The spherical ejecta model with an ejecta mass of Mej = 0.05Msun gives the bolometric luminosity of ~ 2 x 10^42 erg s^-1 at t ~ 0.1 day. We confirm that the existing bolometric and multi-color data of GW170817 can be naturally explained by the purely radioactive model. The expected early UV signals reach 20.5 mag at t ~ 4.3 hours for sources even at 200 Mpc, which is detectable by the facilities such as Swift and the Ultraviolet Transient Astronomy Satellite (ULTRASAT). The early-phase luminosity is sensitive to the structure of the outer ejecta, as also pointed out by Kasen et al. (2017). Therefore, the early UV observations give strong constraints on the structure of the outer ejecta as well as the presence of a heating source besides r-process nuclei.
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