We investigate the Hardy space H 1 L associated with a self-adjoint operator L defined in a general setting in [25]. We assume that there exists an L-harmonic non-negative function h such that the semigroup exp(−tL), after applying the Doob transform related to h, satisfies the upper and lower Gaussian estimates. Under this assumption we describe an illuminating characterisation of the Hardy space H 1 L in terms of a simple atomic decomposition associated with the L-harmonic function h. Our approach also yields a natural characterisation of the BM O-type space corresponding to the operator L and dual to H 1 L in the same circumstances. The applications include surprisingly wide range of operators, such as: Laplace operators with Dirichlet boundary conditions on some domains in R n , Schrödinger operators with certain potentials, and Bessel operators.