We present the Grover adaptive search self-consistent field (GAS-SCF) algorithm. GAS-SCF leverages quantum arithmetic to construct an efficient oracle that marks target states (Fock states) which improve upon some initial classical energy estimate. Amplitude amplification then increases the probability of measuring these states. This approach offers a theoretical quadratic speed-up for the optimization problem encountered in SCF quantum chemistry and establishes a baseline against which structured optimization algorithms, such as QAOA and DQI may be compared. In this work, we classically simulate three examples as proofs of concept of the algorithm, the largest consisting of 26 qubits. We then extend our analysis to two larger systems, with O3 representing the largest case at 330 qubits. These examples are chosen to probe classically challenging SCF regimes. Achieving chemically relevant applications of GAS-SCF will require large-scale, fault-tolerant quantum hardware.
We present the Grover adaptive search self-consistent field (GAS-SCF) algorithm. GAS-SCF leverages quantum arithmetic to construct an efficient oracle that marks target states (Fock states) which improve upon some initial classical energy estimate. Amplitude amplification then increases the probability of measuring these states. This approach offers a theoretical quadratic speed-up for the optimization problem encountered in SCF quantum chemistry and establishes a baseline against which structured optimization algorithms, such as QAOA and DQI may be compared. In this work, we classically simulate three examples as proofs of concept of the algorithm, the largest consisting of 26 qubits. We then extend our analysis to two larger systems, with O3 representing the largest case at 330 qubits. These examples are chosen to probe classically challenging SCF regimes. Achieving chemically relevant applications of GAS-SCF will require large-scale, fault-tolerant quantum hardware.
In quantum chemistry, self-consistent field (SCF) algorithms define a nonlinear optimization problem, with both continuous and discrete components. In this work, we derive Hartree–Fock-inspired SCF algorithms that can be exactly written as a sequence of Quadratic Unconstrained Spin/Binary Optimization problems (QUSO/QUBO). We reformulate the optimization problem as a series of MaxCut graph problems, which can be efficiently solved using semidefinite programming techniques. This procedure provides performance guarantees at each SCF step, irrespective of the complexity of the optimization landscape. We numerically demonstrate the QUBO-SCF and MaxCut-SCF methods by studying the hydroxide anion OH – and molecular Nitrogen N 2 . The largest problem addressed in this study involves a system comprised of 220 qubits (equivalently, spin–orbitals). Our results show that QUBO-SCF and MaxCut-SCF suffer much less from internal instabilities compared with conventional SCF calculations. Additionally, we show that the new SCF algorithms can enhance single-reference methods, such as configuration interaction. Finally, we explore how quantum algorithms for optimization can be applied to the QUSO problems arising from the Hartree–Fock method. Four distinct hybrid-quantum classical approaches are introduced: GAS-SCF, QAOA-SCF, QA-SCF and DQI-SCF.
We present a self-consistent field (SCF) approach within the adaptive derivative-assembled problem-tailored ansatz variational quantum eigensolver (ADAPT-VQE) framework for efficient quantum simulations of chemical systems on near-term quantum computers. To this end, our ADAPT-VQE-SCF approach combines the idea of generating an ansatz with a small number of parameters, resulting in shallow-depth quantum circuits with a direct minimization of an energy expression that is correct to second order with respect to changes in the molecular orbital basis. Our numerical analysis, including calculations for the transition-metal complex ferrocene [Fe (C 5 H 5 ) 2 ], indicates that convergence in the self-consistent orbital optimization loop can be reached without a considerable increase in the number of two-qubit gates in the quantum circuit by comparison to a VQE optimization in the initial molecular orbital basis. Moreover, the orbital optimization can be carried out simultaneously within each iteration of the ADAPT-VQE cycle. ADAPT-VQE-SCF thus allows us to implement a routine analogous to the complete active space SCF, a cornerstone of state-of-the-art computational chemistry, in a hardware-efficient manner on near-term quantum computers. Hence, ADAPT-VQE-SCF paves the way toward a paradigm shift for quantitative quantum-chemistry simulations on quantum computers by requiring fewer qubits and opening up for the use of large and flexible atomic orbital basis sets in contrast to earlier methods that are predominantly based on the idea of full active spaces with minimal basis sets.
In this paper we discuss Grover Adaptive Search (GAS) for Constrained Polynomial Binary Optimization (CPBO) problems, and in particular, Quadratic Unconstrained Binary Optimization (QUBO) problems, as a special case. GAS can provide a quadratic speed-up for combinatorial optimization problems compared to brute force search. However, this requires the development of efficient oracles to represent problems and flag states that satisfy certain search criteria. In general, this can be achieved using quantum arithmetic, however, this is expensive in terms of Toffoli gates as well as required ancilla qubits, which can be prohibitive in the near-term. Within this work, we develop a way to construct efficient oracles to solve CPBO problems using GAS algorithms. We demonstrate this approach and the potential speed-up for the portfolio optimization problem, i.e. a QUBO, using simulation and experimental results obtained on real quantum hardware. However, our approach applies to higher-degree polynomial objective functions as well as constrained optimization problems.
Quantum computers have the potential to solve Quadratic Unconstrained Binary Optimization (QUBO) problems with lower computational complexity than classical ones. Considering the current limitations of quantum hardware, the joint use of classical and quantum paradigms could exploit both advantages. Quantum routines can make some complex tasks for classical computers feasible. For example, in the Grover Adaptive Search (GAS) procedure, the problem cost function is classically shifted iteratively, whenever a negative value is found through the quantum Grover Search (GS) algorithm, until the minimum is achieved. This quantum-classical approach is characterized by many degrees of freedom, e.g. the number of GS iterations in each call and the stop condition of the algorithm, which should be appropriately tuned for an effective and fast convergence to the optimal solution. The availability of software routines could permit the best management of the GAS parameters. This work proposes new mechanisms for GAS parameters management and compares them with the existing ones, like one available in the Qiskit framework. The proposed mechanisms can automatically arrange the parameters according to the algorithm evolution and their previous experience, thus ensuring a more frequent and faster achievement of the optimal solution. Even though these strategies can be further improved, the results are encouraging. The analysis is done to identify the best policy for different problems. It lays the foundation for designing an automatic toolchain for QUBO solving, which can obtain the best possible implementation of the GAS algorithm for each submitted problem.
Abstract This guide is based on the IBM Quantum course Phase Estimation and Factoring and focuses on Grover’s algorithm, a quantum algorithm for unstructured search problems that provides a quadratic speedup over classical approaches. In an unstructured search problem, we are given a function (often represented as an oracle) that marks one or more “correct” solutions among NNN possible candidates. A classical algorithm requires on the order of O(N)O(N)O(N) evaluations in the worst case. In contrast, Grover’s algorithm finds a solution using only O(N)O(\sqrt{N})O(N) oracle queries. This quadratic improvement implies: The quantum algorithm requires roughly the square root of the number of operations needed classically. Any classical algorithm for unstructured search must have cost at least quadratic relative to Grover’s quantum procedure. Core Idea of the Algorithm Grover’s algorithm relies on: Preparation of a uniform superposition (typically using Hadamard gates). An oracle that marks valid solutions via phase inversion. The Grover diffusion operator, which amplifies the probability amplitude of the marked states through interference. By repeatedly applying the Grover operator, the amplitude of the desired solution grows while others diminish, allowing measurement to reveal the correct answer with high probability. Practical Considerations Despite its theoretical elegance and wide applicability, the quadratic speedup of Grover’s algorithm is unlikely to yield near-term practical advantage. Modern classical hardware operates at extremely high clock rates and is vastly more mature than current quantum devices. For problem sizes accessible to today’s quantum computers, classical systems remain dominant. However, history shows that even sub-quadratic classical improvements — such as: Fast Fourier Transform (FFT) Efficient sorting algorithms like quicksort and mergesort have had transformative practical impact. The crucial distinction is that Grover’s algorithm depends on fundamentally different hardware — quantum processors — which are still in early development. Long-Term Perspective As quantum hardware advances in qubit count, coherence time, and error correction, Grover’s quadratic advantage may become practically significant for: Cryptographic key search Optimization heuristics Combinatorial search problems Amplitude amplification subroutines in broader quantum algorithms Through hands-on experimentation on IBM Q, this lesson demonstrates how theoretical amplitude amplification translates into executable quantum circuits, reinforcing the relationship between interference, probability amplitudes, and computational complexity.
The Grover algorithm is a fundamental quantum algorithm that achieves a quadratic speedup for unstructured search problems, requiring O(√N) queries instead of O(N) classically. It works by repeatedly applying an oracle and a diffusion operator to amplify the probability of marked states. This advantage makes it relevant to cryptography, optimization, constraint satisfaction, and as a general primitive via amplitude amplification in areas like quantum machine learning and simulation. However, practical implementations are severely constrained by current Noisy Intermediate Scale Qualtum machines with limited coherence, deep oracle circuits and lack of scalable QRAM, restricting demonstrations to small-scale experiments with reproducibility challenges.