While the diffusion quantum Monte Carlo method (DQMC) is capable, in principle, of calculating exact ground state energies, in practice the fixed-node (FN) approximation leads to node location errors which make FN-DQMC energies upper bounds. It is shown that the node location error can be reduced systematically and without prohibitive increase of computer time requirements by using nodes derived from pair natural orbital CI wave functions (PNO-CI). The reduction is demonstrated for the N atom and the molecules N-2 and H2O. With the DQMC/PNOCI method, we obtain a variational energy of -109.520(3) H for the N-2 molecule and -76.429(1) H for the ground state of the water molecule which is only 22 and 9 mH above the estimated nonrelativistic ground state energy, respectively.