We have found a novel feature of the bistable large-spin model described by the Hamiltonian H 2DS 2 z 2 H x S x . The crossover from thermal to quantum regime for the escape rate can be either first ͑H x , SD͞2͒ or second ͑SD͞2 , H x , 2SD͒ order, that is, sharp or smooth, depending on the strength of the transverse field. This prediction can be tested experimentally in molecular magnets like Mn 12 Ac. [S0031-9007(97)04645-0] PACS numbers: 75.45. + j, 75.50.Tt Transitions between two states in a bistable system can occur either due to the classical thermal activation or via quantum tunneling. A rigorous study of that problem was begun by Kramers [1] and WKB [2][3][4], and a review of the progress that followed can be found in Ref. [5]. At high temperature the transition rate follows the Arrhenius law, G ϳ exp͑2DU͞T͒, with DU being the height of the energy barrier between the two states. In the limit of T ! 0, the transitions are purely quantum, G ϳ exp͑2B͒, with B independent on temperature. Because of the exponential dependence of the thermal rate on T , the temperature T 0 of the crossover from quantum to thermal regime can be estimated as T ͑0͒ 0 DU͞B. For a quasiclassical particle in a potential U͑x͒, Goldanskii [6] noticed the possibility of a more accurate definition, T ͑2͒ 0 "͞t 0 , where t 0 is the period of small oscillations near the bottom of the inverted potential, 2U͑x͒. Below T ͑2͒ 0 , thermally assisted tunneling occurs from the excited levels, that reduces to the tunneling from the ground-state level at T 0. Above T ͑2͒ 0 quantum effects are small and the transitions occur due to the thermal activation to the top of the barrier. Affleck [7] demonstrated that the two regimes smoothly join at T T ͑2͒ 0 . Larkin and Ovchinnikov [8] called this situation the secondorder phase transition from classical to quantum behavior. This means that for G written as G ϳ exp͑2DU͞T eff ͒, the dependence of both T eff and its first derivative on T are continuous at T T ͑2͒ 0 . This situation is not generic, however. The transition between the two regimes can also be of the first order [8,9], i.e., more abrupt, with dT eff ͞dT discontinuous at a certain temperature T ͑1͒ 0 . T ͑2͒ 0 . Chudnovsky derived the criterion allowing one to establish whether first-or second-order transition takes place, based on the shape of the potential U͑x͒. Commonly studied potentials U 2x 2 1 x 4 and U 2x 2 1 x 3 yield the second-order transition. Physically relevant potentials which would exhibit the first-order transitions were not known. In this Letter we show that spin systems readily accessible in the experiment possess both first-and second-order transitions between the classical and quantum behavior of the escape rate. The order of the transition in these systems can be controlled by external magnetic field. Consider a spin system described by the Hamiltonianwhere S ¿ 1. This model is generic for problems of spin tunneling studied by different methods [10 -15]. It is believed to be a good approximation for the molecular magnet...