Splittings of d8 configurations of late-transition metals with EOM-DIP-CCSD and FSCCSD methods.

Multireference methods are usually required for transition metal systems due to the partially filled d electrons. In this work, the single-reference equation-of-motion coupled-cluster method at the singles and doubles level for double ionization potentials (EOM-DIP-CCSD) is employed to calculate energies of states from the d8 configuration of late-transition metal atoms starting from a closed-shell reference. Its results are compared with those from the multireference Fock-space coupled-cluster method at the CCSD level (FSCCSD) for DIP from the same closed-shell reference. Both scalar-relativistic effects and spin-orbit coupling are considered in these calculations. Compared with all-electron FSCCSD results with four-component Dirac-Coulomb Hamiltonian, FSCCSD with relativistic effective core potentials can provide reasonable results, except for atoms with unstable reference. Excitation energies for states in the (n - 1)d8ns2 configuration are overestimated pronouncedly with these two methods, and this overestimation is more severe than those in the (n - 1)d9ns1 configuration. Error of EOM-CCSD on these excitation energies is generally larger than that of FSCCSD. On the other hand, relative energies of most of the states in the d8 configuration with respect to the lowest state in the same configuration are predicted reliably with EOM-DIP-CCSD, except for the 3P0 state of Hg2+ and states in Ir+. FSCCSD can provide reasonable relative energies for the several lowest states, while its error tends to be larger for higher states.

Physics-Constrained Hardware-Efficient Ansatz on Quantum Computers That Is Universal, Systematically Improvable, and Size-Consistent.

Variational wave function ansätze are at the heart of solving quantum many-body problems in physics and chemistry. Previous designs of hardware-efficient ansatz (HEA) on quantum computers are largely based on heuristics and lack rigorous theoretical foundations. In this work, we introduce a physics-constrained approach for designing HEA with rigorous theoretical guarantees by imposing a few fundamental constraints. Specifically, we require that the target HEA to be universal, systematically improvable, and size-consistent, which is an important concept in quantum many-body theories for scalability but has been overlooked in previous designs of HEA. We extend the notion of size-consistency to HEA and present a concrete realization of HEA that satisfies all these fundamental constraints while only requiring linear qubit connectivity. The developed physics-constrained HEA is superior to other heuristically designed HEA in terms of both accuracy and scalability, as demonstrated numerically for the Heisenberg model and some typical molecules. In particular, we find that restoring size-consistency can significantly reduce the number of layers needed to reach a certain accuracy. In contrast, the failure of other HEA to satisfy these constraints severely limits their scalability to larger systems with more than 10 qubits. Our work highlights the importance of incorporating physical constraints into the design of HEA for efficiently solving many-body problems on quantum computers.