Low-frequency spin dynamics in the S = 1/2 antiferromagnetic spin-chain compound α-VO(PO3)2 has been studied by means of 31 P NMR. The nuclear spin-lattice relaxation rate 1/T1 at the P site exhibits H −1/2 dependence on the applied magnetic field (H) at temperatures (T ) well above the intrachain coupling strength J/kB = 3.50 K indicating one-dimensional diffusive spin dynamics. The diffusive contribution to 1/T1 decreases on cooling as electronic spins acquire short-range antiferromagnetic correlations within the chain, and vanishes almost entirely around T ≈ J/kB. This is accompanied by an apparent increase of the spin-diffusion constant from the value expected in the classical limit. On the other hand, the field-independent part of 1/T1 increases with decreasing temperature, which may be a precursor for the true long-range antiferromagnetic ordering found below TN = 1.93 ± 0.01 K.KEYWORDS: α-VO(PO 3 ) 2 , NMR, antiferromagnetic spin chain, nuclear spin relaxation, spin diffusion §1. Introduction There has been a continued interest in the dynamics of low-dimensional quantum antiferromagnets at finite temperatures. One of the issues which has attracted renewed attention is a problem of spin diffusion in the one-dimensional (1D) Heisenberg spin chain. It is argued from phenomenology that at high enough temperatures and at long times, the spin autocorrelation function of the 1D Heisenberg spin chain has a diffusive formleading to divergence of the spectral density at low frequencies as ω −1/2 . However, because the diffusive form (1.1) is not derived from the microscopic Hamiltonian but is a consequence of the hydrodynamical assumption for the spin-spin correlation, 1) the question on the existence of spin diffusion in 1D spin chains has been studied intensively from both theoretical and experimental viewpoints. One of the best studied theoretical models is the S = 1/2 XXZ chain represented by the Hamiltonian 2, 3, 4, 5, 6, 7)(1.2)At the isotropic point (∆ = 1) and at low enough temperatures (T ≪ J/k B ), analytical expressions for the dynamical susceptibility χ(q, ω) have been derived for q ≈ 0 and π, and are shown to have no diffusive pole at low frequencies.2) At modestly high, or much higher temperatures compared with the intrachain coupling strength J, the problem is still controversial. Although the absence * E-mail: kikuchi@ph.noda.sut.ac.jp of diffusive excitations seems to be settled for the XXZ chain with planar anisotropy (0 ≤ ∆ < 1), a definite answer for the absence (or presence) of spin diffusion at the isotropic point has not yet been given.Diffusive behavior of the spin-spin correlation has been observed experimentally in several 1D spin chains via the ω −1/2 resonance-frequency dependence of the nuclear spin-lattice relaxation rate 1/T 1 at elevated temperatures. 8,9,10,11,12,13) As to the S = 1/2 chain, an analysis of the ω dependence of 1/T 1 at the Cu site in Sr 2 CuO 3 based on the classical spin-diffusion theory gives an unusually high value of the spin diffusion constant compared with the ...