We report the results of 27 Al-NMR measurements on a single crystal of PrTi 2 Al 20 . This compound shows a phase transition near 2 K associated with the quadrupole degree of freedom of Pr ions, for which the ground state of the crystalline electric field is a nonmagnetic doublet. When a magnetic field is applied along the 111 direction, the NMR lines split upon entering the low-temperature phase, indicating the breaking of the three fold rotation symmetry due to the field-induced magnetic dipole perpendicular to the field. This provides microscopic evidence for a ferro order of the O 20 quadrupole. Although a first-order transition is expected theoretically, the line splitting evolves continuously within the experimental resolution.KEYWORDS: PrTi 2 Al 20 , NMR, quadrupole order, symmetry breaking Multipoles of f electrons in rare-earth compounds show a wide variety of phenomena. [1][2][3][4] In particular, non-Kramers rare-earth ions with an even number of f electrons in a cubic environment have been attracting strong interest recently. [5][6][7][8][9][10][11] In these systems, it is possible that the ground states of the J multiplet split by the cubic crystalline electric field (CEF) are nonmagnetic, i.e., the matrix elements of the magnetic dipole J are identically zero, yet have a degeneracy that allows active higher-order multipoles such as electric quadrupoles or magnetic octupoles. Then various interesting phenomena such as multipole orders [12][13][14] or multichannel Kondo effects 15,16) are expected at low temperatures.These possibilities have indeed been realized in compounds containing Pr 3+ ions with the 4 f 2 electronic configuration. The nine states of the J = 4 ground multiplet are split by a cubic CEF into the Γ 1 nonmagnetic singlet, the Γ 3 nonmagnetic doublet, the Γ 4 magnetic triplet, and the Γ 5 magnetic triplet. If the CEF ground state is the Γ 3 doublet, we encounter an interesting situation that the ground state is nonmagnetic but has nonzero matrix elements for the two types of quadrupoles, O 20 = (3J 2 z −J 2 )/2 and O 22 = √ 3(J 2 x −J 2 y )/2, and one octupole T xyz = ( √ 15/6)J x J y J z , where the bar represents the sum over the possible permutations of the indices x, y, and z. 13) The series of compounds PrT 2 X 20 (T : transition metal, X: Zn or Al) provides particularly interesting examples of the Γ 3 CEF ground states. 4) As shown in Fig. 1 [18][19][20][21] all of which also show superconductivity. [21][22][23][24][25][26] Various measurements indicate that the Al-based materials are characterized by stronger hybridization between conduction and f electrons than the Zn-based materials, leading to anomalous transport properties and their pronounced pressure depen- * E-mail : taka.taniguchi@issp.u-tokyo.ac.jp dence. 4,[23][24][25][26][27][28][29][30] In this paper, we focus on PrTi 2 Al 20 . The magnetic susceptibility for H 111 is nearly independent of temperature below 20 K, indicating van Vleck paramagnetism with a nonmagnetic CEF ground state. 29) Specific heat measurements ...