Estimating vibrational entropy is a significant challenge in thermodynamics and statistical mechanics due to its reliance on quantum mechanical properties. This paper introduces a quantum algorithm designed to estimate vibrational entropy via energy derivatives. Our approach block encodes the exact expression for the second derivative of the energy and uses quantum linear systems algorithms to deal with the reciprocal powers of the gaps that appear in the expression. We further show that if prior knowledge about the values of the second derivative is used then our algorithm can $ε$-approximate the entropy using a number of queries that scales with the condition number $κ$, the temperature $T$, error tolerance $ε$ and an analogue of the partition function $\mathcal{Z}$, as $\widetilde{O}\left(\frac{\mathcal{Z}κ^2 }{εT}\right)$. We show that if sufficient prior knowledge is given about the second derivative then the query scales quadratically better than these results. This shows that, under reasonable assumptions of the temperature and a quantum computer can be used to compute the vibrational contributions to the entropy faster than analogous classical algorithms would be capable of. Our findings highlight the potential of quantum algorithms to enhance the prediction of thermodynamic properties, paving the way for advancements in fields such as material science, molecular biology, and chemical engineering.
Estimating vibrational entropy is a significant challenge in thermodynamics and statistical mechanics due to its reliance on quantum mechanical properties. This paper introduces a quantum algorithm designed to estimate vibrational entropy via energy derivatives. Our approach block encodes the exact expression for the second derivative of the energy and uses quantum linear systems algorithms to deal with the reciprocal powers of the gaps that appear in the expression. We further show that if prior knowledge about the values of the second derivative is used then our algorithm can ε-approximate the entropy using a number of queries that scales with the condition number κ, the temperature T, error tolerance ε and an analogue of the partition function Z, as O(εTZκ2). We show that if sufficient prior knowledge is given about the second derivative then the query scales quadratically better than these results. This shows that, under reasonable assumptions of the temperature and a quantum computer can be used to compute the vibrational contributions to the entropy faster than analogous classical algorithms would be capable of. Our findings highlight the potential of quantum algorithms to enhance the prediction of thermodynamic properties, paving the way for advancements in fields such as material science, molecular biology, and chemical engineering.
While most work on the quantum simulation of chemistry has focused on computing energy surfaces, a similarly important application requiring subtly different algorithms is the computation of energy derivatives. Almost all molecular properties can be expressed an energy derivative, including molecular forces, which are essential for applications such as molecular dynamics simulations. Here, we introduce new quantum algorithms for computing molecular energy derivatives with significantly lower complexity than prior methods. Under cost models appropriate for noisy-intermediate scale quantum devices, we demonstrate how low-rank factorization and other tomography schemes can be optimized for energy derivative calculations. We numerically demonstrate that our techniques reduce the number of circuit repetitions required by many orders of magnitude for even modest systems, and that the cost of estimating an entire force vector may in some systems be lower than the cost of estimating the energy. In the context of fault-tolerant algorithms, we develop new methods of estimating energy derivatives with Heisenberg limited scaling, incorporating state-of-the-art techniques for block encoding fermionic operators. In contrast to our near-term results, we find that the cost of estimating forces with any of our Heisenberg-limited methods is bounded by the cost of estimating energies, due to inner loops requiring either energy estimation or reflections around the ground state. This implies that applications such as geometry optimization, coupling parameter estimation, and spectral prediction may be practical on fault-tolerant quantum devices, but tractable molecular dynamics simulations of large-scale systems requires further algorithmic advances.
Abstract Accurately computing the free energies of biological processes is a cornerstone of computer-aided drug design, but it is a daunting task. The need to sample vast conformational spaces and account for entropic contributions makes the estimation of binding free energies very expensive. While classical methods, such as thermodynamic integration and alchemical free energy calculations, have significantly contributed to reducing computational costs, they still face limitations in terms of efficiency and scalability. We tackle this through a quantum algorithm for the estimation of free energy differences by adapting the existing Liouvillian approach and introducing several key algorithmic improvements. We directly implement the Liouvillian operator and provide an efficient description of electronic forces acting on both nuclear and electronic particles on the quantum ground state potential energy surface. This leads to super-polynomial runtime scaling improvements in the precision of our Liouvillian simulation approach and quadratic improvements in the scaling with the number of particles relative to prior quantum algorithms. Second, our algorithm calculates free energy differences via a fully quantum implementation of thermodynamic integration and alchemy, thereby foregoing expensive entropy estimation subroutines used in prior works. Our results open new avenues towards the application of quantum computers in drug discovery.
We present classical and quantum algorithms for approximating partition functions of classical Hamiltonians at a given temperature. Our work has two main contributions: first, we modify the classical algorithm of Stefankovic, Vempala and Vigoda (J. ACM, 56(3), 2009) to improve its sample complexity; second, we quantize this new algorithm, improving upon the previously fastest quantum algorithm for this problem, due to Harrow and Wei (SODA 2020). The conventional approach to estimating partition functions requires approximating the means of Gibbs distributions at a set of inverse temperatures that form the so-called cooling schedule. The length of the cooling schedule directly affects the complexity of the algorithm. Combining our improved version of the algorithm of Stefankovic, Vempala and Vigoda with the paired-product estimator of Huber (Ann. Appl. Probab., 25(2), 2015), our new quantum algorithm uses a shorter cooling schedule than previously known. This length matches the optimal length conjectured by Stefankovic, Vempala and Vigoda. The quantum algorithm also achieves a quadratic advantage in the number of required quantum samples compared to the number of random samples drawn by the best classical algorithm, and its computational complexity has quadratically better dependence on the spectral gap of the Markov chains used to produce the quantum samples.
We give classical and quantum algorithms for approximating partition functions of classical Hamiltonians at a given temperature. Specifically, we modify the classical algorithm of Štefankovič, Vempala and Vigoda (J. ACM, 56(3), 2009) to improve its sample complexity; and we quantize this new algorithm, improving upon the previously best quantum algorithm for computing Gibbs partition functions due to Harrow and Wei (SODA 2020).The conventional approach to estimate partition functions requires approximating the mean of Gibbs distributions at nearby inverse temperatures that satisfy certain properties; this set of temperatures is called a cooling schedule. The length of the cooling schedule directly affects the complexity of the algorithm. Combining our improved version of the algorithm of Štefankovič, Vempala and Vigoda with the paired-product estimator of Huber (Ann. Appl. Probab., 25(2), 2015), our new quantum algorithm uses a shorter cooling schedule than previously known. This length matches the optimal length conjectured by Štefankovič, Vempala and Vigoda. The quantum algorithm also achieves a quadratic advantage in the number of required quantum samples compared to the number of random samples drawn by the best classical algorithm, and its computational complexity has quadratically better dependence on the spectral gap of the Markov chains used to produce the quantum samples.
Entropy estimation of discrete probability distributions is a fundamental problem in statistical inference and quantum property estimation. In this paper, we study the problem of estimating Rényi entropy Hα(p) for any distribution p=(pi)i=1n given its purified quantum query-access. For non-integer α>1, our algorithm estimates Hα(p) to within additive error ε using only O(nmax{1/2,1−1/α}/ε) queries, which improves the best known upper bound for dependence on both n and 1/ε. For 0<α<1, our algorithm has query complexity O(n1/(2α)/εmax{1,1/(2α)}), which improves the dependence on 1/ε of the current best upper bound without incresing its n dependence. Our approach adapts the multi-level estimation framework to relative approximation of the power sums and leverage binary search to remove the requirement of prior knowledge of them. We also strengthen the precision-dependent lower bound to Ω(1/εmax{1,1/(2α)}) for 0<α<1, which identifies the optimal precision dependence of our algorithm.
We present a novel quantum algorithm for estimating Gibbs partition functions in sublinear time with respect to the logarithm of the size of the state space. This is the first speed-up of this type to be obtained over the seminal nearly-linear time algorithm of Štefankovič, Vempala and Vigoda [45]. Our result also preserves the quadratic speed-up in precision and spectral gap achieved in previous work by exploiting the properties of quantum Markov chains. As an application, we obtain new polynomial improvements over the best-known algorithms for computing the partition function of the Ising model, counting the number of k-colorings, matchings or independent sets of a graph, and estimating the volume of a convex body. Our approach relies on developing new variants of the quantum phase and amplitude estimation algorithms that return nearly unbiased estimates with low variance and without destroying their initial quantum state. We extend these subroutines into a nearly unbiased quantum mean estimator that reduces the variance quadratically faster than the classical empirical mean. No such estimator was known to exist prior to our work. These properties, which are of general interest, lead to better convergence guarantees within the paradigm of simulated annealing for computing partition functions. * The full version of the paper can be accessed at http://arxiv.org/abs/2207.08643.