The Ground State Electronic Energy of Benzene

Abstract

We report on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground state energy of the benzene molecule in a standard correlation-consistent basis set of double-$\zeta$ quality. As a broad international endeavour, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory. In our assessment, the evaluated high-level methods are all found to qualitatively agree on a final correlation energy, with most methods yielding an estimate of the FCI value around $-863$ m$E_{\text{H}}$. However, we find the root-mean-square deviation of the energies from the studied methods to be considerable (1.3 m$E_{\text{H}}$), which in light of the acclaimed performance of each of the methods for smaller molecular systems clearly displays the challenges faced in extending reliable, near-exact correlation methods to larger systems. While the discrepancies exposed by our study thus emphasize the fact that the current state-of-the-art approaches leave room for improvement, we still expect the present assessment to provide a valuable community resource for benchmark and calibration purposes going forward.

arXiv comment29 pages, 1 figure, 2 tables. SI as an ancillary file

References in corpus (36)

• Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
• Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
• Solutions of the Two Dimensional Hubbard Model: Benchmarks and Results from a Wide Range of Numerical Algorithms
• Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
• A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks
• A deterministic alternative to the full configuration interaction quantum Monte Carlo method
• The density matrix renormalization group for ab initio quantum chemistry
• A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry
• Controlling the accuracy of the density matrix renormalization group method: The Dynamical Block State Selection approach
• An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
• Towards the solution of the many-electron problem in real materials: equation of state of the hydrogen chain with state-of-the-art many-body methods
• Cheap and near exact CASSCF with large active spaces
• Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method
• Semistochastic Projector Monte Carlo Method
• CASSCF with Extremely Large Active Spaces using the Adaptive Sampling Configuration Interaction Method
• Excited states using semistochastic heat-bath configuration interaction
• Fast Semistochastic Heat-Bath Configuration Interaction
• Selected configuration interaction dressed by perturbation
• New Approaches for ab initio Calculations of Molecules with Strong Electron Correlation
• Efficient heat-bath sampling in Fock space
• Direct comparison of many-body methods for realistic electronic Hamiltonians
• Virtual orbital many-body expansions: A possible route towards the full configuration interaction limit
• Unbiasing the initiator approximation in Full Configuration Interaction Quantum Monte Carlo
• Many-Body Expanded Full Configuration Interaction. I. Weakly Correlated Regime
• Many-Body Expanded Full Configuration Interaction. II. Strongly Correlated Regime
• Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments and parallel distribution
• Full Coupled-Cluster Reduction for Accurate Description of Strong Electron Correlation
• Generalized Many-Body Expanded Full Configuration Interaction Theory
• Coordinate descent full configuration interaction
• An efficient and accurate perturbative correction to initiator full configuration interaction quantum Monte Carlo
• Linked Coupled Cluster Monte Carlo
• Preconditioning and perturbative estimators in full configuration interaction quantum Monte Carlo
• Cluster decomposition of full configuration interaction wave functions: a tool for chemical interpretation of systems with strong correlation
• The performance of phaseless auxiliary-field quantum Monte Carlo on the ground state electronic energy of benzene
• An efficient deterministic perturbation theory for selected configuration interaction methods
• A hybrid approach to extending selected configuration interaction and full configuration interaction quantum Monte Carlo

Cited by in corpus (71)

• The Variational Quantum Eigensolver: a review of methods and best practices
• Combining Machine Learning and Computational Chemistry for Predictive Insights Into Chemical Systems
• A Quantum Computing View on Unitary Coupled Cluster Theory
• Block2: a comprehensive open source framework to develop and apply state-of-the-art DMRG algorithms in electronic structure and beyond
• Quantum Power Method by a Superposition of Time-Evolved States
• Low communication high performance ab initio density matrix renormalization group algorithms
• Quantum-centric Supercomputing for Materials Science: A Perspective on Challenges and Future Directions
• Prospects of Quantum Computing for Molecular Sciences
• The Shape of Full Configuration Interaction to Come
• How will quantum computers provide an industrially relevant computational advantage in quantum chemistry?
• Towards the ground state of molecules via diffusion Monte Carlo on neural networks
• Overlap-ADAPT-VQE: Practical Quantum Chemistry on Quantum Computers via Overlap-Guided Compact Ansätze
• The performance of CIPSI on the ground state electronic energy of benzene
• Matrix product states with large sites
• The Adaptive Shift Method in Full Configuration Interaction Quantum Monte Carlo: Development and Applications
• Transcorrelated Density Matrix Renormalization Group
• Accurate full configuration interaction correlation energy estimates for five- and six-membered rings
• Reference Energies for Valence Ionizations and Satellite Transitions
• How accurate are EOM-CC4 vertical excitation energies?
• Reference Energies for Cyclobutadiene: Automerization and Excited States
• Reference CC3 Excitation Energies for Organic Chromophores: Benchmarking TD-DFT, BSE/$GW$ and Wave Function Methods
• Quantum correlations in molecules: from quantum resourcing to chemical bonding
• State-Specific Coupled-Cluster Methods for Excited States
• Quantum simulations employing connected moments expansions
• SOiCI and iCISO: Combining iterative configuration interaction with spin-orbit coupling in two ways
• Ground- and Excited-State Dipole Moments and Oscillator Strengths of Full Configuration Interaction Quality
• Molecular Excited State Calculations with Adaptive Wavefunctions on a Quantum Eigensolver Emulation: Reducing Circuit Depth and Separating Spin States
• Is Externally Corrected Coupled Cluster Always Better than the Underlying Truncated Configuration Interaction?
• The Effect of Geometry, Spin and Orbital Optimization in Achieving Accurate, Fully-Correlated Results for Iron-Sulfur Cubanes
• Incremental Treatments of the Full Configuration Interaction Problem
• Extension of selected configuration interaction for transcorrelated methods
• Hydrogenation of small aromatic heterocycles at low temperatures
• Towards near-exact solutions of molecular electronic structure: Full coupled-cluster reduction with a second-order perturbative correction
• Ground and Excited State First-Order Properties in Many-Body Expanded Full Configuration Interaction Theory
• Extending GPU-Accelerated Gaussian Integrals in the TeraChem Software Package to f Type Orbitals: Implementation and Applications
• Vibrational Heat-Bath Configuration Interaction
• High-Level Coupled-Cluster Energetics by Monte Carlo Sampling and Moment Expansions: Further Details and Comparisons
• Cluster many-body expansion: a many-body expansion of the electron correlation energy about a cluster mean-field reference
• Taming the fixed-node error in diffusion Monte Carlo via range separation
• Benchmark Phaseless Auxiliary-Field Quantum Monte Carlo Method for Small Molecules
• Simulation of adiabatic quantum computing for molecular ground states
• The Quantum House Of Cards
• Spin-adapted selected configuration interaction in a determinant basis
• A Parallel, Distributed Memory Implementation of the Adaptive Sampling Configuration Interaction Method
• Multicomponent Heat-Bath Configuration Interaction with the Perturbative Correction for the Calculation of Protonic Excited States
• Mean-Field Density Matrix Decompositions
• Hybrid Auxiliary Field Quantum Monte Carlo for Molecular Systems
• Rationale for the Extrapolation Procedure in Selected Configuration Interaction
• MBE-CASSCF Approach for the Accurate Treatment of Large Active Spaces
• Hybrid Tree Tensor Networks for quantum simulation
• Phaseless auxiliary field quantum Monte Carlo with projector-augmented wave method for solids
• Mapping renormalized coupled cluster methods to quantum computers through a compact unitary representation of non-unitary operators
• Renormalized Internally-Contracted Multireference Coupled Cluster with Perturbative Triples
• Selected Configuration Interaction for Resonances
• Interpolating many-body wave functions for accelerated molecular dynamics on the near-exact electronic surface
• Can G4-like Composite Ab Initio Methods Accurately Predict Vibrational Harmonic Frequencies?
• Compactification of Determinant Expansions via Transcorrelation
• Tensorized orbitals for computational chemistry
• Complete Active Space Iterative Coupled Cluster Theory
• Self-Refinement of Auxiliary-Field Quantum Monte Carlo via Non-Orthogonal Configuration Interaction
• Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states
• A truncated Davidson method for the efficient "chemically accurate" calculation of full configuration interaction wavefunctions without any large matrix diagonalization
• Critical Limitations in Quantum-Selected Configuration Interaction Methods
• Fixed and partial-node approximations in Slater determinant space for molecules
• Full Configuration Interaction Excited-State Energies in Large Active Spaces from Subspace Iteration with Repeated Random Sparsification
• PASPT2: a size-extensive and size-consistent partial-active-space multi-state multi-reference second-order perturbation theory for strongly correlated electrons
• iCISCF: An Iterative Configuration Interaction-based Multiconfigurational Self-consistent Field Theory for Large Active Spaces
• High-Level Coupled-Cluster Energetics by Merging Moment Expansions with Selected Configuration Interaction
• Further Development of iCIPT2 for Strongly Correlated Electrons
• Feasibility of performing quantum chemistry calculations on quantum computers
• Electronic excited states in deep variational Monte Carlo