Quantum self-consistent equation-of-motion method for computing molecular excitation energies, ionization potentials, and electron affinities on a quantum computer.

Near-term quantum computers are expected to facilitate material and chemical research through accurate molecular simulations. Several developments have already shown that accurate ground-state energies for small molecules can be evaluated on present-day quantum devices. Although electronically excited states play a vital role in chemical processes and applications, the search for a reliable and practical approach for routine excited-state calculations on near-term quantum devices is ongoing. Inspired by excited-state methods developed for the unitary coupled-cluster theory in quantum chemistry, we present an equation-of-motion-based method to compute excitation energies following the variational quantum eigensolver algorithm for ground-state calculations on a quantum computer. We perform numerical simulations on H2, H4, H2O, and LiH molecules to test our quantum self-consistent equation-of-motion (q-sc-EOM) method and compare it to other current state-of-the-art methods. q-sc-EOM makes use of self-consistent operators to satisfy the vacuum annihilation condition, a critical property for accurate calculations. It provides real and size-intensive energy differences corresponding to vertical excitation energies, ionization potentials and electron affinities. We also find that q-sc-EOM is more suitable for implementation on NISQ devices as it is expected to be more resilient to noise compared with the currently available methods.

Symmetry Breaking Slows Convergence of the ADAPT Variational Quantum Eigensolver.

Because quantum simulation of molecular systems is expected to provide the strongest advantage over classical computing methods for systems exhibiting strong electron correlation, it is critical that the performance of VQEs be assessed for strongly correlated systems. For classical simulation, strong correlation often results in symmetry breaking of the Hartree-Fock reference, leading to Löwdin's well-known "symmetry dilemma", whereby accuracy in the energy can be increased by breaking spin or spatial symmetries. Here, we explore the impact of symmetry breaking on the performance of ADAPT-VQE using two strongly correlated systems: (i) the "fermionized" anisotropic Heisenberg model, where the anisotropy parameter controls the correlation in the system, and (ii) symmetrically stretched linear H4, where correlation increases with increasing H-H separation. In both of these cases, increasing the level of correlation of the system leads to spontaneous symmetry breaking (parity and S^2, respectively) of the mean-field solutions. We analyze the role that symmetry breaking in the reference states and orbital mappings of the fermionic Hamiltonians have in the compactness and performance of ADAPT-VQE. We observe that improving the energy of the reference states by breaking symmetry has a deleterious effect on ADAPT-VQE by increasing the length of the ansatz necessary for energy convergence and exacerbating the problem of "gradient troughs".

Is the Trotterized UCCSD Ansatz Chemically Well-Defined?

The variational quantum eigensolver (VQE) has emerged as one of the most promising near-term quantum algorithms that can be used to simulate many-body systems such as molecular electronic structures. Serving as an attractive ansatz in the VQE algorithm, unitary coupled cluster (UCC) theory has seen a renewed interest in recent literature. However, unlike the original classical UCC theory, implementation on a quantum computer requires a finite-order Suzuki-Trotter decomposition to separate the exponentials of the large sum of Pauli operators. While previous literature has recognized the nonuniqueness of different orderings of the operators in the Trotterized form of UCC methods, the question of whether or not different orderings matter at the chemical scale has not been addressed. In this Letter, we explore the effect of operator ordering on the Trotterized UCCSD ansatz, as well as the much more compact k-UpCCGSD ansatz recently proposed by Lee et al. [ J. Chem. Theory Comput. , 2019 , 15 , 311 . arXiv, 2019 , quant-ph:1909.09114. https://arxiv.org/abs/1909.09114 ]. We observe a significant, system-dependent variation in the energies of Trotterizations with different operator orderings. The energy variations occur on a chemical scale, sometimes on the order of hundreds of kcal/mol. This Letter establishes the need to define not only the operators present in the ansatz but also the order in which they appear. This is necessary for adhering to the quantum chemical notion of a "model chemistry", in addition to the general importance of scientific reproducibility. As a final note, we suggest a useful strategy to select out of the combinatorial number of possibilities, a single well-defined and effective ordering of the operators.

Toward Long-Range Entanglement between Electrically Driven Single-Molecule Magnets.

Over the past two decades, several molecules have been explored as possible building blocks of a quantum computer, a device that would provide exponential speedups for a number of problems, including the simulation of large, strongly correlated chemical systems. Achieving strong interactions and entanglement between molecular qubits remains an outstanding challenge. Here, we show that the TbPc2 single-molecule magnet has the potential to overcome this obstacle because of its sensitivity to electric fields stemming from the hyperfine Stark effect. We show how this feature can be leveraged to achieve long-range entanglement between pairs of molecules using a superconducting resonator as a mediator. Our results suggest that the molecule-resonator interaction is near the edge of the strong-coupling regime and could potentially pass into it given a more detailed, quantitative understanding of the TbPc2 molecule.

Deterministic Generation of Large-Scale Entangled Photonic Cluster State from Interacting Solid State Emitters.

The ability to create large highly entangled "cluster" states is crucial for measurement-based quantum computing. We show that deterministic multiphoton entanglement can be created from coupled solid state quantum emitters without the need for any two-qubit gates and regardless of whether the emitters are identical. In particular, we present a general method for controlled entanglement creation by making direct use of the always-on exchange interaction, in combination with single-qubit operations. This is used to provide a recipe for the generation of two-dimensional, cluster-state entangled photons that can be carried out with existing experimental capabilities in quantum dots.

An adaptive variational algorithm for exact molecular simulations on a quantum computer.

Quantum simulation of chemical systems is one of the most promising near-term applications of quantum computers. The variational quantum eigensolver, a leading algorithm for molecular simulations on quantum hardware, has a serious limitation in that it typically relies on a pre-selected wavefunction ansatz that results in approximate wavefunctions and energies. Here we present an arbitrarily accurate variational algorithm that, instead of fixing an ansatz upfront, grows it systematically one operator at a time in a way dictated by the molecule being simulated. This generates an ansatz with a small number of parameters, leading to shallow-depth circuits. We present numerical simulations, including for a prototypical strongly correlated molecule, which show that our algorithm performs much better than a unitary coupled cluster approach, in terms of both circuit depth and chemical accuracy. Our results highlight the potential of our adaptive algorithm for exact simulations with present-day and near-term quantum hardware.

Spin-photon entanglement interfaces in silicon carbide defect centers.

Optically active spins in solid-state systems can be engineered to emit photons that are entangled with the spin in the solid. This allows for applications such as quantum communications, quantum key distribution, and distributed quantum computing. Recently, there has been a strong interest in silicon carbide defects, as they emit very close to the telecommunication wavelength, making them excellent candidates for long range quantum communications. In this work we develop explicit schemes for spin-photon entanglement in several SiC defects: the silicon monovacancy, the silicon divacancy, and the NV center in SiC. Distinct approaches are given for (i) single-photon and spin entanglement and (ii) the generation of long strings of entangled photons. The latter are known as cluster states and comprise a resource for measurement-based quantum information processing.

Spin-cavity interactions between a quantum dot molecule and a photonic crystal cavity.

The integration of InAs/GaAs quantum dots into nanophotonic cavities has led to impressive demonstrations of cavity quantum electrodynamics. However, these demonstrations are primarily based on two-level excitonic systems. Efforts to couple long-lived quantum dot electron spin states with a cavity are only now succeeding. Here we report a two-spin-cavity system, achieved by embedding an InAs quantum dot molecule within a photonic crystal cavity. With this system we obtain a spin singlet-triplet Λ-system where the ground-state spin splitting exceeds the cavity linewidth by an order of magnitude. This allows us to observe cavity-stimulated Raman emission that is highly spin-selective. Moreover, we demonstrate the first cases of cavity-enhanced optical nonlinearities in a solid-state Λ-system. This provides an all-optical, local method to control the spin exchange splitting. Incorporation of a highly engineerable quantum dot molecule into the photonic crystal architecture advances prospects for a quantum network.

Optical control of coherent interactions between electron spins in InGaAs quantum dots.

Coherent interactions between spins in quantum dots are a key requirement for quantum gates. We have performed pump-probe experiments in which pulsed lasers emitting at different photon energies manipulate two distinct subsets of electron spins within an inhomogeneous InGaAs quantum dot ensemble. The spin dynamics are monitored through their precession about an external magnetic field. These measurements demonstrate spin precession phase shifts and modulations of the magnitude of one subset of oriented spins after optical orientation of the second subset. The observations are consistent with results from a model using a Heisenberg-like interaction with µeV strength.

Electron-nuclear dynamics in a quantum dot under nonunitary electron control.

We introduce a method for solving the problem of an externally controlled electron spin in a quantum dot interacting with host nuclei via the hyperfine interaction. Our method accounts for generalized (nonunitary) evolution effected by external controls and the environment, such as coherent lasers combined with spontaneous emission. As a concrete example, we develop the microscopic theory of the dynamics of nuclear-induced frequency focusing as first measured in Science 317, 1896 (2007); we find that the nuclear relaxation rates are several orders of magnitude faster than those quoted in that work.

Optically generated 2-dimensional photonic cluster state from coupled quantum dots.

We propose a method to generate a two-dimensional cluster state of polarization encoded photonic qubits from two coupled quantum dot emitters. We combine the proposal for generating one-dimensional cluster state strings from a single dot, with a new proposal for an induced conditional phase gate between the two quantum dots. The entanglement between the two dots translates to entanglement between the two photonic cluster state strings. Further interpair coupling of the quantum dots using cavities and waveguides can lead to a two-dimensional cluster sheet, the importance of which stems from the fact that it is a universal resource for quantum computation. Analysis of errors indicates that our proposal is feasible with current technology. Crucially, the emitted photons need not have identical frequencies, and so there are no constraints on the resonance energies for the quantum dots.

Directing nuclear spin flips in InAs quantum dots using detuned optical pulse trains.

We find that detuning an optical pulse train from electronic transitions in quantum dots controls the direction of nuclear spin flips. The optical pulse train generates electron spins that precess about an applied magnetic field, with a spin component parallel to the field only for detuned pulses. This component leads to asymmetry in the nuclear spin flips, providing a way to stabilize and control the nuclear spin polarization. This effect is observed using two-color, time-resolved Faraday rotation and ellipticity.

Optical spin initialization and nondestructive measurement in a quantum dot molecule.

The spin of an electron in a self-assembled InAs/GaAs quantum dot molecule is optically prepared and measured through the trion triplet states. A longitudinal magnetic field is used to tune two of the trion states into resonance, forming a superposition state through asymmetric spin exchange. As a result, spin-flip Raman transitions can be used for optical spin initialization, while separate trion states enable cycling transitions for nondestructive measurement. With two-laser transmission spectroscopy we demonstrate both operations simultaneously, something not previously accomplished in a single quantum dot.

Selective optical control of electron spin coherence in singly charged GaAs-Al0.3Ga0.7As quantum dots.

Coherent transient excitation of the spin ground states in singly charged quantum dots creates optically coupled and decoupled states of the electron spin. We demonstrate selective excitation from the spin ground states to the trion state through phase sensitive control of the spin coherence via these three states, leading to partial rotations of the spin vector. This progress lays the ground work for achieving complete ultrafast spin rotations.

Theory of fast optical spin rotation in a quantum dot based on geometric phases and trapped states.

A method is proposed for the optical rotation of the spin of an electron in a quantum dot using excited trion states to implement operations significantly faster than those of most existing proposals. Key ingredients are the geometric phase induced by 2pi hyperbolic secant pulses, use of coherently trapped states and use of naturally dark states. Our proposal covers a variety of quantum dots by addressing different parameter regimes. Numerical simulations with typical parameters for InAs self-assembled quantum dots, including their dissipative dynamics, give fidelities of the operations in excess of 99%.

Stimulated and spontaneous optical generation of electron spin coherence in charged GaAs quantum dots.

We report on the coherent optical excitation of electron spin polarization in the ground state of charged GaAs quantum dots via an intermediate charged exciton (trion) state. Coherent optical fields are used for the creation and detection of the Raman spin coherence between the spin ground states of the charged quantum dot. The measured spin decoherence time, which is likely limited by the nature of the spin ensemble, approaches 10 ns at zero field. We also show that the Raman spin coherence in the quantum beats is caused not only by the usual stimulated Raman interaction but also by simultaneous spontaneous radiative decay of either excited trion state to a coherent combination of the two spin states.