Quantum computers have emerged as a promising platform to simulate strong electron correlation that is crucial to catalysis and photochemistry. However, owing to the choice of a trial wave function employed in the variational quantum eigensolver (VQE) algorithm, accurate simulation is restricted to certain classes of correlated phenomena. Herein, we combine the spin-flip (SF) formalism with the unitary coupled cluster with singles and doubles (UCCSD) method via the quantum equation-of-motion (qEOM) approach to allow for an efficient simulation of a large family of strongly correlated problems. We show that the developed qEOM-SF-UCCSD/VQE method outperforms its UCCSD/VQE counterpart for simulation of the cis – trans isomerization of ethylene, and the automerization of cyclobutadiene and the predicted qEOM-SF-UCCSD/VQE barrier heights are in a good agreement with the experimentally determined values. The developments presented herein will further stimulate the investigation of this approach for simulations of other types of correlated/entangled phenomena on quantum computers.
Quantum computers have emerged as a promising platform to simulate strong electron correlation that is crucial to catalysis and photochemistry. However, owing to the choice of a trial wave function employed in the variational quantum eigensolver (VQE) algorithm, accurate simulation is restricted to certain classes of correlated phenomena. Herein, we combine the spin-flip (SF) formalism with the unitary coupled cluster with singles and doubles (UCCSD) method via the quantum equation-of-motion (qEOM) approach to allow for an efficient simulation of a large family of strongly correlated problems. We show that the developed qEOM-SF-UCCSD/VQE method outperforms its UCCSD/VQE counterpart for simulation of the cis – trans isomerization of ethylene, and the automerization of cyclobutadiene and the predicted qEOM-SF-UCCSD/VQE barrier heights are in a good agreement with the experimentally determined values. The developments presented herein will further stimulate the investigation of this approach for simulations of other types of correlated/entangled phenomena on quantum computers.
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.
Simulation of electronic structure is one of the most promising applications on noisy intermediate-scale quantum (NISQ) era devices. However, NISQ devices suffer from a number of challenges like limited qubit connectivity, short coherence times, and sizable gate error rates. Thus, desired quantum algorithms should require shallow circuit depths and low qubit counts to take advantage of these devices. Here, we attempt to reduce quantum resource requirements for molecular simulations on a quantum computer while maintaining the desired accuracy with the help of classical quantum chemical theories of canonical transformation and explicit correlation. In this work, compact ab initio Hamiltonians are generated classically, in the second quantized form, through an approximate similarity transformation of the Hamiltonian with (a) an explicitly correlated two-body unitary operator with generalized pair excitations that remove the Coulombic electron-electron singularities from the Hamiltonian and (b) a unitary one-body operator to efficiently capture the orbital relaxation effects required for accurate description of the excited states. The resulting transcorrelated Hamiltonians are able to describe both the ground and the excited states of molecular systems in a balanced manner. Using the variational quantum eigensolver (VQE) method based on the unitary coupled cluster with singles and doubles (UCCSD) ansatz and only a minimal basis set (ANO-RCC-MB), we demonstrate that the transcorrelated Hamiltonians can produce ground state energies comparable to the reference CCSD energies with the much larger cc-pVTZ basis set. This leads to a reduction in the number of required CNOT gates by more than 3 orders of magnitude for the chemical species studied in this work. Furthermore, using the quantum equation of motion (qEOM) formalism in conjunction with the transcorrelated Hamiltonian, we are able to reduce the deviations in the excitation energies from the reference EOM-CCSD/cc-pVTZ values by an order of magnitude. The transcorrelated Hamiltonians developed here are Hermitian and contain only one- and two-body interaction terms and thus can be easily combined with any quantum algorithm for accurate electronic structure simulations.
The variational quantum eigensolver (VQE) algorithm combined with the unitary coupled cluster (UCC) ansatz has been developed for the quantum computation of molecular energies and wave functions within the Born–Oppenheimer approximation. Herein, this approach is extended to multicomponent systems to enable the quantum mechanical treatment of more than one type of particle, such as electrons and positrons or electrons and nuclei, without invoking the Born–Oppenheimer approximation. Specifically, we introduce the multicomponent unitary coupled cluster (mcUCC) method combined with the VQE algorithm for the calculation of ground-state energies and wave functions as well as the multicomponent equation-of-motion (mcEOM) method for the calculation of excitation energies. These methods are developed within the nuclear-electronic orbital (NEO) framework and are formulated in the qubit basis to enable implementations on quantum computers. Moreover, these methods are used to calculate the ground-state energy and excitation energies of positronium hydride, where both electrons and the positron are treated quantum mechanically, as well as the H 2 molecule, where both electrons and one proton are treated quantum mechanically. These applications validate the implementation and provide benchmark data for future calculations. The errors due to Trotterization of the mcUCC ansatz are also analyzed. This formalism, as well as the accompanying computer code, will serve as the basis for applications to more complex multicomponent systems, such as simulations of photoinduced nonadiabatic molecular processes, on both classical and quantum computers.
In the field of polaritonic chemistry, strong light-matter interactions are used to alter chemical reactions inside optical cavities. To understand these processes, the development of reliable theoretical models is essential. While traditional methods have to balance accuracy and system size, new developments in quantum computing offer a path for accurate calculations on currently available quantum devices. Here, we introduce the quantum electrodynamics unitary coupled cluster (QED-UCC) method combined with the Variational Quantum Eigensolver algorithm, as well as the quantum electrodynamics equation-of-motion (QED-EOM) method formulated in the qubit basis that allow accurate calculations of ground-state and excited-state properties of strongly coupled light-matter systems suitable for quantum computers. These methods show excellent agreement with the exact reference results and can outperform their traditional counterparts when strong electronic correlations become significant. This work sets the stage for future developments of polaritonic quantum chemistry methods suitable for both classical and quantum computers.
Simulating molecules using the Variational Quantum Eigensolver method is one of the promising applications for NISQ-era quantum computers. Designing an efficient ansatz to represent the electronic wave function is crucial in such simulations. Standard unitary coupled-cluster with singles and doubles (UCCSD) ansatz tends to have a large number of insignificant terms that do not lower the energy of the system. In this work, we present a unitary selective coupled-cluster method, a way to construct a unitary coupled-cluster ansatz iteratively using a selection procedure with excitations up to fourth order. This approach uses the electronic Hamiltonian matrix elements and the amplitudes for excitations already present in the ansatz to find the important excitations of higher order and to add them to the ansatz. The important feature of the method is that it systematically reduces the energy error with increasing ansatz size for a set of test molecules. {The main advantage of the proposed method is that the effort to increase the ansatz does not require any additional measurements on a quantum computer.}
The factorized form of unitary coupled cluster theory (UCC) is a promising wave-function ansatz for the variational quantum eigensolver algorithm. Here, we present a quantum-inspired classical algorithm for UCC based on an exact operator identity for the individual UCC factors. We implement this algorithm for calculations of the H 10 linear chain and the H 2 O molecule with single and double ζ basis sets to provide insights into UCC as a wave-function ansatz. We find that for weakly correlated molecules, the factorized form of the UCC provides similar accuracy to conventional coupled cluster theory (CC); for strongly correlated molecules, where CC often breaks down, UCC significantly outperforms the configuration interaction (CI) ansatz. As a result, the factorized form of the UCC is an accurate, efficient, and reliable electronic structure method in both the weakly and strongly correlated regions. This classical algorithm now allows robust benchmarking of anticipated results from quantum computers and application of coupled-cluster techniques to more strongly correlated molecules.