Over the past two decades, unconventional superconductivity with gap symmetry other than s-wave has been found in several classes of materials, including heavy fermion (HF), high-T_c, and organic superconductors. Unconventional superconductivity is characterized by anisotropic superconducting gap functions, which may have zeros (nodes) along certain directions in the Brillouin zone. The nodal structure is closely related to the pairing interaction, and it is widely believed that the presence of nodes is a signature of magnetic or some other exotic, rather than conventional phonon-mediated, pairing mechanism. Therefore experimental determination of the gap function is of fundamental importance. However, the detailed gap structure, especially the direction of the nodes, is an unresolved issue in most unconventional superconductors. Recently it has been demonstrated that the thermal conductivity and specific heat measurements under magnetic field rotated relative to the crystal axes are a powerful method for determining the shape of the gap and the nodal directions in the bulk. Here we review the theoretical underpinnings of the method and the results for the nodal structure of several unconventional superconductors, including borocarbide YNi$_2$B$_2$C, heavy fermions UPd$_2$Al$_3$, CeCoIn$_5$, and PrOs$_4$Sb$_{12}$, organic superconductor, $kappa$-(BEDT-TTF)$_2$Cu(NCS)$_2$, and ruthenate Sr$_2$RuO$_4$, determined by angular variation of the thermal conductivity and heat capacity.
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