Quantum Chemistry in the Age of Quantum Computing

Practical challenges in simulating quantum systems on classical computers have been widely recognized in the quantum physics and quantum chemistry communities over the past century. Although many approximation methods have been introduced, the complexity of quantum mechanics remains hard to appease. The advent of quantum computation brings new pathways to navigate this challenging complexity landscape. By manipulating quantum states of matter and taking advantage of their unique features such as superposition and entanglement, quantum computers promise to efficiently deliver accurate results for many important problems in quantum chemistry such as the electronic structure of molecules. In the past two decades significant advances have been made in developing algorithms and physical hardware for quantum computing, heralding a revolution in simulation of quantum systems. This article is an overview of the algorithms and results that are relevant for quantum chemistry. The intended audience is both quantum chemists who seek to learn more about quantum computing, and quantum computing researchers who would like to explore applications in quantum chemistry.Comment: 194 pages, 13 figures, 5 tables and 404 references. Fixed formatting issues from the previous version. Comments welcom

Compact wavefunctions from compressed imaginary time evolution

Simulation of quantum systems promises to deliver physical and chemical predictions for the frontiers of technology. Unfortunately, the exact representation of these systems is plagued by the exponential growth of dimension with the number of particles, or colloquially, the curse of dimensionality. The success of approximation methods has hinged on the relative simplicity of physical systems with respect to the exponentially complex worst case. Exploiting this relative simplicity has required detailed knowledge of the physical system under study. In this work, we introduce a general and efficient black box method for many-body quantum systems that utilizes technology from compressed sensing to find the most compact wavefunction possible without detailed knowledge of the system. It is a Multicomponent Adaptive Greedy Iterative Compression (MAGIC) scheme. No knowledge is assumed in the structure of the problem other than correct particle statistics. This method can be applied to many quantum systems such as spins, qubits, oscillators, or electronic systems. As an application, we use this technique to compute ground state electronic wavefunctions of hydrogen fluoride and recover 98% of the basis set correlation energy or equivalently 99.996% of the total energy with $50$ configurations out of a possible $10^7$. Building from this compactness, we introduce the idea of nuclear union configuration interaction for improving the description of reaction coordinates and use it to study the dissociation of hydrogen fluoride and the helium dimer

Hypercomputability of quantum adiabatic processes: Fact versus Prejudices

We give an overview of a quantum adiabatic algorithm for Hilbert's tenth problem, including some discussions on its fundamental aspects and the emphasis on the probabilistic correctness of its findings. For the purpose of illustration, the numerical simulation results of some simple Diophantine equations are presented. We also discuss some prejudicial misunderstandings as well as some plausible difficulties faced by the algorithm in its physical implementation.Comment: 25 pages, 4 figures. Invited paper for a special issue of the Journal of Applied Mathematics and Computatio

Exploring connections between statistical mechanics and Green's functions for realistic systems. Temperature dependent electronic entropy and internal energy from a self-consistent second-order Green's function

Including finite-temperature effects from the electronic degrees of freedom in electronic structure calculations of semiconductors and metals is desired; however, in practice it remains exceedingly difficult when using zero-temperature methods, since these methods require an explicit evaluation of multiple excited states in order to account for any finite-temperature effects. Using a Matsubara Green's function formalism remains a viable alternative, since in this formalism it is easier to include thermal effects and to connect the dynamic quantities such as the self-energy with static thermodynamic quantities such as the Helmholtz energy, entropy, and internal energy. However, despite the promising properties of this formalism, little is know about the multiple solutions of the non-linear equations present in the self-consistent Matsubara formalism and only a few cases involving a full Coulomb Hamiltonian were investigated in the past. Here, to shed some light onto the iterative nature of the Green's function solutions, we self-consistently evaluate the thermodynamic quantities for a one-dimensional (1D) hydrogen solid at various interatomic separations and temperatures using the self-energy approximated to second-order (GF2). At many points in the phase diagram of this system, multiple phases such as a metal and an insulator exist, and we are able to determine the most stable phase from the analysis of Helmholtz energies. Additionally, we show the evolution of the spectrum of 1D boron nitride (BN) to demonstrate that GF2 is capable of qualitatively describing the temperature effects influencing the size of the band gap

Ultrafast ab-initio Quantum Chemistry Using Matrix Product States

Ultrafast dynamics in chemical systems provide a unique access to fundamental processes at the molecular scale. A proper description of such systems is often very challenging because of the quantum nature of the problem. The concept of matrix product states (MPS), however, has proven its performance in describing such correlated quantum system in recent years for a wide range of applications. In this work, we continue the development of the MPS approach to study ultrafast electron dynamics in quantum chemical systems. The method combines time evolution schemes, such as fourth-order Runge-Kutta and Krylov space time evolution, with MPS, in order to solve the time-dependent Schr\"odinger equation efficiently. This allows for describing electron dynamics in molecules on a full configurational interaction (CI) level for a few femtoseconds after excitation. As a benchmark, we compare MPS based calculations to full CI calculations for a chain of hydrogen atoms and for the water molecule. Krylov space time evolution is in particular suited for the MPS approach, as it provides a wide range of opportunities to be adjusted to the reduced MPS dimension case. Finally, we apply the MPS approach to describe charge migration effects in iodoacetylene and find direct agreement between our results and experimental observations

Computational Theory of a splitting BEC using a Generalized Wannier basis I: Theory and Statics

We investigate the behavior of a Bose-Einstein Condensate (BEC) under the influence of a central barrier as the particle number trends towards the thermodynamic limit. In order to perform these studies, we present a novel method which is tractable in the large-$N$ limit. This method employs what may be considered to be a generalized Wannier basis, which successfully incorporates features of previous theoretical and computational assays to the splitting problem, including mean field effects, and has access to the dimensionality, trap parameters, and particle numbers relevant to recent experiments. At any barrier height we are able to discern between a two-mode state and a state which is described sufficiently by mean field theory and, further, give a criterion and technique for matching the two-mode theory to the zero-barrier state. We compare the basis used in this model to the de-localized basis functions underlying alternate models used in recent theoretical work on the double-well splitting problem and show that only the generalized Wannier basis displays the level crossing and emergence of two complex order parameters with overall $U(1) \oplus U(1)$ symmetry as expected from a large-$N$ analogue of the Superfluid to Mott insulator transition. Using this model, we identify a universal structure, independent of $N$, in this phase transition. We also present an analytic and model-independent description of this universal structure and discuss its consequences for realizing true two-mode physics with a BEC which trends towards the thermodynamic limit.Comment: 29 pages, 8 figure

Electron-pair densities with time-dependent quantum Monte-Carlo

In this paper we use sets of de Broglie-Bohm trajectories to describe the quantum correlation effects which take place between the electrons in helium atom due to exchange and Coulomb interactions. A short-range screening of the Coulomb potential is used to modify the repulsion between the same spin electrons in physical space in order to comply with the Pauli's exclusion principle. By calculating the electron-pair density for ortho-helium we found that the shape of the exchange hole can be controlled uniquely by a simple screening parameter. For para-helium the inter-electronic distance, and hence the Coulomb hole, results from the combined action of the Coulomb repulsion and the non-local quantum correlations. In this way a robust and self-interaction-free approach is presented to find both the ground state and the time evolution of non-relativistic quantum systems.Comment: 18 pages, 4 figure

Many-body state engineering using measurements and fixed unitary dynamics

We develop a scheme to prepare a desired state or subspace in high-dimensional Hilbert-spaces using repeated applications of a single static projection operator onto the desired target and fixed unitary dynamics. Benchmarks against other control schemes, performed on generic Hamiltonians and on Bose-Hubbard systems, establish the competitiveness of the method. As a concrete application of the control of mesoscopic atomic samples in optical lattices we demonstrate the near deterministic preparation of Schr\"{o}dinger cat states of all atoms residing on either the odd or the even sites.Comment: 5 pages, 4 figures, New revised version with new title, added references, corrected typos and unclaritie

Q# and NWChem: Tools for Scalable Quantum Chemistry on Quantum Computers

Fault-tolerant quantum computation promises to solve outstanding problems in quantum chemistry within the next decade. Realizing this promise requires scalable tools that allow users to translate descriptions of electronic structure problems to optimized quantum gate sequences executed on physical hardware, without requiring specialized quantum computing knowledge. To this end, we present a quantum chemistry library, under the open-source MIT license, that implements and enables straightforward use of state-of-art quantum simulation algorithms. The library is implemented in Q#, a language designed to express quantum algorithms at scale, and interfaces with NWChem, a leading electronic structure package. We define a standardized schema for this interface, Broombridge, that describes second-quantized Hamiltonians, along with metadata required for effective quantum simulation, such as trial wavefunction ansatzes. This schema is generated for arbitrary molecules by NWChem, conveniently accessible, for instance, through Docker containers and a recently developed web interface EMSL Arrows. We illustrate use of the library with various examples, including ground- and excited-state calculations for LiH, H$_{10}$, and C$_{20}$ with an active-space simplification, and automatically obtain resource estimates for classically intractable examples.Comment: 36 pages, 5 figures. Examples and data in ancillary files folde

Quantum Implementation of Unitary Coupled Cluster for Simulating Molecular Electronic Structure

In classical computational chemistry, the coupled-cluster ansatz is one of the most commonly used $ab~initio$ methods, which is critically limited by its non-unitary nature. The unitary modification as an ideal solution to the problem is, however, extremely inefficient in classical conventional computation. Here, we provide the first experimental evidence that indeed the unitary version of the coupled cluster ansatz can be reliably performed in physical quantum system, a trapped ion system. We perform a simulation on the electronic structure of a molecular ion (HeH$^+$), where the ground-state energy surface curve is probed, energies of excited-states are studied and the bond-dissociation is simulated non-perturbatively. Our simulation takes advantages from quantum computation to overcome the intrinsic limitations in classical computation and our experimental results indicate that the method is promising for preparing molecular ground-states for quantum simulation.Comment: 6 pages, 4 figure