A new implementation of the density matrix renormalization group is presented for ab initio quantum chemistry. Test computations have been performed of the dissociation energies of the diatomics Be2, N2, HF. A preliminary calculation on the Cr2 molecule provides a new variational upper bound to the ground state energy.

We have compared different strategies for ab initio quantum chemistry density matrix renormalization group treatments. The two starting orbital blocks include all valence and active orbitals of the reference complete active space self consistent field wave function. To generate the remaining blocks, we propose following the order of the contributions to the correlation energy: a posteriori using approximate occupation numbers or a priori, using a Møller–Plesset type of arguments, by explicit evaluation of second-order interactions. We have compared two different schemes for orbital localization to identify the important and less important orbital interactions and simplify the generation of the orbital blocks. To truncate the expansion we have compared two approaches, keeping constant the number m of components or the threshold λ to fix the residue of the expansion at each step. The extrapolation of the energies is found to provide accurate estimates of the full configuration interaction energy, making the expansion independent on the actual values of the two parameters m and λ. We propose to generate the factors for the two blocks from ground and excited eigenvectors of the Hamiltonian matrix.

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