In this article we show that every geodesic is rank one and the Hessian of Busemann functions is positive definite for a harmonic Damek-Ricci space, a two step solvable Lie group with a left invariant metric. Moreover, the eigenspace of the Hessian of Busemann functions on a Hadamard manifold (M, g) corresponding to eigenvalue zero is investigated with respect to rank of geodesics. On a harmonic Hadamard manifold which is of purely exponential volume growth, or of hypergeometric type it is shown that every Busemann function admits positive definite Hessian. A criterion for (M, g) fulfilling visibility axiom is presented in terms of positive definiteness of the Hessian of Busemann functions.