A quantum algorithm for spin chemistry: a Bayesian exchange coupling parameter calculator with broken-symmetry wave functions.

The Heisenberg exchange coupling parameter J (H = -2J S i · S j ) characterises the isotropic magnetic interaction between unpaired electrons, and it is one of the most important spin Hamiltonian parameters of multi-spin open shell systems. The J value is related to the energy difference between high-spin and low-spin states, and thus computing the energies of individual spin states are necessary to obtain the J values from quantum chemical calculations. Here, we propose a quantum algorithm, B̲ayesian ex̲change coupling parameter calculator with b̲roken-symmetry wave functions (BxB), which is capable of computing the J value directly, without calculating the energies of individual spin states. The BxB algorithm is composed of the quantum simulations of the time evolution of a broken-symmetry wave function under the Hamiltonian with an additional term j S 2, the wave function overlap estimation with the SWAP test, and Bayesian optimisation of the parameter j. Numerical quantum circuit simulations for H2 under a covalent bond dissociation, C, O, Si, NH, OH+, CH2, NF, O2, and triple bond dissociated N2 molecule revealed that the BxB can compute the J value within 1 kcal mol-1 of errors with less computational costs than conventional quantum phase estimation-based approaches.