Related papers: Orthogonally Constrained CASSCF Framework: Newton-…
In the Noisy Intermediate-Scale Quantum (NISQ) era, solving the electronic structure problem from chemistry is considered as the "killer application" for near-term quantum devices. In spite of the success of variational hybrid…
The computation of excited states within the Complete Active Space Self-Consistent Field (CASSCF) framework remains a significant challenge in quantum chemistry, both theoretically and algorithmically. In this work, we extend the K\"ahler…
An analytical gradient theory for single-state N-electron valence state perturbation theory (NEVPT2), using both strongly contracted (SC) and partially contracted (PC) internal contraction schemes, is developed. We demonstrate the utility…
In this paper we consider a nonconvex unconstrained optimization problem minimizing a twice differentiable objective function with H\"older continuous Hessian. Specifically, we first propose a Newton-conjugate gradient (Newton-CG) method…
Electric field-assisted chemistry has attracted much attention in recent years, particularly in the context of oriented external electric fields for controlling molecular structure and reactivity. Such fields have been explored in a wide…
Bonding in the C$_2$ molecule is investigated with CAS(8,8) wave functions using canonical MOs. In a subsequent step, orthogonal atomic orbitals are constructed by localizing the CASSCF MOs on the two carbon atoms with an orthogonal…
This paper presents a novel natural gradient and Hessian-free (NGHF) optimisation framework for neural network training that can operate efficiently in a distributed manner. It relies on the linear conjugate gradient (CG) algorithm to…
We propose a stochastic variance-reduced cubic regularized Newton method for non-convex optimization. At the core of our algorithm is a novel semi-stochastic gradient along with a semi-stochastic Hessian, which are specifically designed for…
We consider the problem of minimizing a non-convex function over a smooth manifold $\mathcal{M}$. We propose a novel algorithm, the Orthogonal Directions Constrained Gradient Method (ODCGM) which only requires computing a projection onto a…
An energy functional for orbital based $O(N)$ calculations is proposed, which depends on a number of non orthogonal, localized orbitals larger than the number of occupied states in the system, and on a parameter, the electronic chemical…
We use the recently-developed Heat-bath Configuration Interaction (HCI) algorithm as an efficient active-space solver to perform multi-configuration self-consistent field calculations (HCISCF) with large active spaces. We give a detailed…
The multiscale model combining the multiconfigurational self-consistent field (MCSCF) method with the fully atomistic polarizable Fluctuating Charges (FQ) force field (J. Chem. Theory Comput. 2024, 20, 9954-9967) is here extended to the…
We present a real-space formulation and higher-order finite-difference implementation of periodic Orbital-free Density Functional Theory (OF-DFT). Specifically, utilizing a local reformulation of the electrostatic and kernel terms, we…
The analytic energy gradients in the atomic orbital representation have recently been published (J. Chem. Phys. 146, 014102, 2017) within the framework of the natural orbital functional theory (NOFT). We provide here an alternative…
An algorithm is devised for solving minimization problems with equality constraints. The algorithm uses first-order derivatives of both the objective function and the constraints. The step is computed as a sum between a steepest-descent…
This paper describes a method for solving smooth nonconvex minimization problems subject to bound constraints with good worst-case complexity guarantees and practical performance. The method contains elements of two existing methods: the…
Designing quantum circuits for ground state preparation is a fundamental task in quantum information science. However, standard Variational Quantum Algorithms (VQAs) are often constrained by limited ansatz expressivity and difficult…
In this paper, we propose objective-function-free (OFF) variants of the proximal Newton method for nonconvex composite optimization problems and the regularized Newton method for unconstrained optimization problems, respectively, using…
We propose an orbital optimized method for unitary coupled cluster theory (OO-UCC) within the variational quantum eigensolver (VQE) framework for quantum computers. OO-UCC variationally determines the coupled cluster amplitudes and also…
This paper investigates the box-constrained $\ell_0$-regularized sparse optimization problem. We introduce the concept of a $\tau$-stationary point and establish its connection to the local and global minima of the box-constrained…