The unitary coupled cluster (UCC) approach has been one of the most popular wavefunction parametrizations for the variational quantum eigensolver due to the relative ease of optimization compared to hardware-efficient ansätze. In this contribution, we explore the energy landscape of the unitary coupled cluster singles and doubles (UCCSD) wavefunction for two commonly employed benchmark systems, lithium hydride and the nitrogen dimer. We investigate the organization of the solution space in terms of local minima and show how it changes as the number and order of operators of the UCC ansatz are varied. Surprisingly, we find that in all cases, the UCCSD energy has numerous low-lying minima connected by high energy transition states. Additionally, the energy spread of the minima that lie in the same band as the global minimum may exceed chemical accuracy, making the location of the true global minimum especially challenging.
The unitary coupled cluster (UCC) approach has been one of the most popular wavefunction parametrizations for the variational quantum eigensolver due to the relative ease of optimization compared to hardware-efficient ansätze. In this contribution, we explore the energy landscape of the unitary coupled cluster singles and doubles (UCCSD) wavefunction for two commonly employed benchmark systems, lithium hydride and the nitrogen dimer. We investigate the organization of the solution space in terms of local minima and show how it changes as the number and order of operators of the UCC ansatz are varied. Surprisingly, we find that in all cases, the UCCSD energy has numerous low-lying minima connected by high energy transition states. Additionally, the energy spread of the minima that lie in the same band as the global minimum may exceed chemical accuracy, making the location of the true global minimum especially challenging.
The Coupled Cluster (CC) method is used to compute the electronic correlation energy in atoms and molecules and often leads to highly accurate results. However, due to its single-reference nature, standard CC in its projected form fails to describe quantum states characterized by strong electronic correlations and multi-reference projective methods become necessary. On the other hand, quantum algorithms for the solution of many-electron problems have also emerged recently. The quantum unitary variant of CC (UCC) with singles and doubles (q-UCCSD) is a popular wavefunction Ansatz for the variational quantum eigensolver algorithm. The variational nature of this approach can lead to significant advantages compared to its classical equivalent in the projected form, in particular, for the description of strong electronic correlation. However, due to the large number of gate operations required in q-UCCSD, approximations need to be introduced in order to make this approach implementable in a state-of-the-art quantum computer. In this work, we evaluate several variants of the standard q-UCCSD Ansatz in which only a subset of excitations is included. In particular, we investigate the singlet and pair q-UCCD approaches combined with orbital optimization. We show that these approaches can capture the dissociation/distortion profiles of challenging systems, such as H4, H2O, and N2 molecules, as well as the one-dimensional periodic Fermi–Hubbard chain. These results promote the future use of q-UCC methods for the solution of challenging electronic structure problems in quantum chemistry.
The recent quantum information boom has effected a resurgence of interest in the unitary coupled cluster (UCC) theory. Our group’s interest in local energy landscapes of unitary ansätze prompted us to investigate the classical approach of truncating the Taylor series expansion (instead of a perturbative expansion) of the UCC with singles and doubles (UCCSD) energy at the second order. This amounts to an approach where the electron correlation energy is estimated by taking a single Newton–Raphson step from Hartree–Fock toward UCCSD. Such an approach has been explored previously, but the accuracy was not extensively studied. In this paper, we investigate the performance and observe similar pathologies to the linearized coupled cluster with singles and doubles. We introduce the use of derivatives of order three or greater to help partially recover the variational lower bound of true UCCSD, restricting these derivatives to those of the “unmixed” category in order to simplify the model. By testing the approach on several potential energy surfaces and reaction energies, we find this “diagonal” approximation to higher order terms to be effective at reducing sensitivity near singularities for strongly correlated regimes, while not significantly diminishing the accuracy of weakly correlated systems.
Unitary coupled cluster (UCC), originally developed as a variational alternative to the popular traditional coupled cluster method, has seen a resurgence as a functional form for use on quantum computers. However, the number of excitors present in the Ansatz often presents a barrier to implementation on quantum computers. Given the natural sparsity of wavefunctions obtained from quantum Monte Carlo methods, we consider here a stochastic solution to the UCC problem. Using the coupled cluster Monte Carlo framework, we develop cluster selection schemes that capture the structure of the UCC wavefunction, as well as its Trotterized approximation, and use these to solve the corresponding projected equations. Due to the fast convergence of the equations with order in the cluster expansion, this approach scales polynomially with the size of the system. Unlike traditional UCC implementations, our approach naturally produces a non-variational estimator for the energy in the form of the projected energy. For unitary coupled cluster singles and doubles (UCCSD) in small systems, we find that this agrees well with the expectation value of the energy and, in the case of two electrons, with full configuration interaction results. For the larger N2 system, the two estimators diverge, with the projected energy approaching the coupled cluster result, while the expectation value is close to results from traditional UCCSD.
One of the commonly used chemically inspired approaches in variational quantum computing is the unitary coupled-cluster (UCC) ansätze. Despite being a systematic way of approaching the exact limit, the number of parameters in the standard UCC ansätze exhibits unfavorable scaling with respect to the system size, hindering its practical use on near-term quantum devices. Efforts have been taken to propose some variants of the UCC ansätze with better scaling. In this paper, we explore the parameter redundancy in the preparation of unitary coupled-cluster singles and doubles (UCCSD) ansätze employing spin-adapted formulation, small amplitude filtration, and entropy-based orbital selection approaches. Numerical results of using our approach on some small molecules have exhibited a significant cost reduction in the number of parameters to be optimized and in the time to convergence compared with conventional UCCSD-VQE simulations. We also discuss the potential application of some machine learning techniques in further exploring the parameter redundancy, providing a possible direction for future studies.
Unitary coupled cluster (UCC), originally developed as a variational alternative to the popular traditional coupled cluster method, has seen a resurgence as a functional form for use on quantum computers. However, the number of excitors present in the Ansatz often presents a barrier to implementation on quantum computers. Given the natural sparsity of wavefunctions obtained from quantum Monte Carlo methods, we consider here a stochastic solution to the UCC problem. Using the coupled cluster Monte Carlo framework, we develop cluster selection schemes that capture the structure of the UCC wavefunction, as well as its Trotterized approximation, and use these to solve the corresponding projected equations. Due to the fast convergence of the equations with order in the cluster expansion, this approach scales polynomially with the size of the system. Unlike traditional UCC implementations, our approach naturally produces a non-variational estimator for the energy in the form of the projected energy. For unitary coupled cluster singles and doubles (UCCSD) in small systems, we find that this agrees well with the expectation value of the energy and, in the case of two electrons, with full configuration interaction results. For the larger N2 system, the two estimators diverge, with the projected energy approaching the coupled cluster result, while the expectation value is close to results from traditional UCCSD.
Quantum computation represents a revolutionary approach to solving problems in quantum chemistry. However, due to the limited quantum resources in the current noisy intermediate-scale quantum (NISQ) devices, quantum algorithms for large chemical systems remain a major task. In this work, we demonstrate that the circuit depth of the unitary coupled cluster (UCC) and UCC-based ansatzes in the algorithm of the variational quantum eigensolver can be significantly reduced by an energy-sorting strategy. Specifically, subsets of excitation operators are first prescreened from the operator pool according to its contribution to the total energy. The quantum circuit ansatz is then iteratively constructed until convergence of the final energy to a typical accuracy. For demonstration, this method has been successfully applied to molecular and periodic systems. Particularly, a reduction of 50%-98% in the number of operators is observed while retaining the accuracy of the original UCCSD operator pools. This method can be straightforwardly extended to general parametric variational ansatzes.