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Let \\(\\hat{f}_m\\) denote the approximation to \\(f(A)v\\) given the Krylov-like subspace method and let \\(E_m(f)=f(A)v-\\hat{f}_m\\) be the corresponding error. By introducing certain functions \\(\\phi_k(z)\\) defined recursively from \\(f(z)\\), a series expansion to the error \\(E_m(f)\\) is derived and in this way an old result by Saad on the Arnoldi approximation to the matrix exponential times a vector is generalized. An important contribution of the paper is to show that the first term of such an expansion provides a reliable estimate to the error. Particular emphasis is devoted to the matrix exponential and to Hermitian matrices. Some numerical examples are presented to confirm that the proposed a posteriori error estimates are effective at least for the matrix exponential, matrix cosine and matrix sine functions.  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