Graph-based block-diagonalization of full configuration interaction Hamiltonian: H$_2$ chains study

Abstract: We developed a graph-based block-diagonalization (GBBD) method for the full configuration interaction Hamiltonian of molecular systems to efficiently calculate the exact eigenvalues of low-energy states. In this approach, the non-zero matrix elements of the Hamiltonian are represented as edges on a graph, which naturally decomposes into disconnected clusters. Each cluster corresponds to an independent block in the block-diagonalized form of the Hamiltonian. The eigenvalues in the low-energy sector were obtained by solving the eigenvalue problem for each block matrix and by solving a modified Hamiltonian subject to orthonormality constraints with respect to previously computed lower-energy eigenstates. We applied the GBBD method to linear hydrogen H chains ranging from H$2$ to H${12}$. The results showed excellent agreement with exact ones, confirming both the accuracy and efficiency of the proposed method. Finally, we discussed several physical properties with respect to the number of H$_2$ molecules.