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## ABSTRACT

We introduce a unitary coupled-cluster (UCC) ansatz termed $k$-UpCCGSD that is based on a family of sparse generalized doubles (D) operators which provides an affordable and systematically improvable unitary coupled-cluster wavefunction suitable for implementation on a near-term quantum computer. $k$-UpCCGSD employs $k$ products of the exponential of pair coupled-cluster double excitation operators (pCCD), together with generalized single (S) excitation operators. We compare its performance in both efficiency of implementation and accuracy with that of the generalized UCC ansatz employing the full generalized SD excitation operators (UCCGSD), as well as with the standard ansatz employing only SD excitations (UCCCSD). $k$-UpCCGSD is found to show the best scaling for quantum computing applications, requiring a circuit depth of $\mathcal O(kN)$, compared with $\mathcal O(N^3)$ for UCCGSD and $\mathcal O((N-\eta)^2 \eta)$ for UCCSD where $N$ is the number of spin orbitals and $\eta$ is the number of electrons. We analyzed the accuracy of these three ans\"atze by making classical benchmark calculations on the ground state and the first excited state of H$_4$ (STO-3G, 6-31G), H$_2$O (STO-3G), and N$_2$ (STO-3G), making additional comparisons to conventional coupled cluster methods. The results for ground states show that $k$-UpCCGSD offers a good tradeoff between accuracy and cost, achieving chemical accuracy for lower cost of implementation on quantum computers than both UCCGSD and UCCSD. Excited states are calculated with an orthogonally constrained variational quantum eigensolver approach. This is seen to generally yield less accurate energies than for the corresponding ground states. We demonstrate that using a specialized multi-determinantal reference state constructed from classical linear response calculations allows these excited state energetics to be improved.