Related papers: Analytical Nuclear Gradients for State-Averaged Co…
While configuration interaction singles (CIS) provides a computationally efficient description of excited states, it systematically overestimates excitation energies and performs poorly for strongly correlated systems, partly due to the…
We present analytic gradients and derivative couplings for the simplest possible multireference configuration interaction method, CIS-1D, an electronic structure ansatz that includes all single excitations and one lone double excitation on…
In a recent work, we introduced the foundations of an orthogonally constrained complete active space self-consistent field (OC-CASSCF) framework that produces state-specific molecular orbitals for mutually orthogonal multiconfigurational…
We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed…
Hierarchy configuration interaction (hCI) has been recently introduced as an alternative configuration interaction (CI) route combining excitation degree and seniority number, which showed to efficiently recover both dynamic and static…
The second-order multireference driven similarity renormalization group perturbation theory (DSRG-MRPT2) theory provides an efficient means of correcting the dynamical correlation with the multiconfiguration reference function. The…
An accurate description of electron correlation is one of the most challenging problems in quantum chemistry. The exact electron correlation can be obtained by means of full configuration interaction (FCI). A simple strategy for…
The accurate description of electron correlation is a central challenge in computational chemistry, with selected configuration interaction (SCI) emerging as a powerful tool to approach the full CI limit. While recent machine learning (ML)…
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…
Elucidating photochemical reactions is vital to understand various biochemical phenomena and develop functional materials such as artificial photosynthesis and organic solar cells, albeit its notorious difficulty by both experiments and…
The combinatorial scaling of configuration interaction (CI) has long restricted its applicability to only the simplest molecular systems. Here, we report the first numerically exact CI calculation exceeding one quadrillion ($10^{15}$)…
In this paper, we study the nuclear gradients of heat bath configuration interaction self-consistent field (HCISCF) wave functions and use them to optimize molecular geometries for various molecules. We show that the HCISCF nuclear…
We study several approaches to orbital optimization in selected configuration interaction plus perturbation theory (SCI+PT) methods, and test them on the ground and excited states of three molecules using the semistochastic heatbath…
We introduce state-averaging into the method of Monte Carlo configuration interaction (SA-MCCI) to allow the stable and efficient calculation of excited states. We show that excited potential curves for H$_{3}$, including a crossing with…
We introduce and benchmark a systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI), \alert{which is a particular realization of multiconfigurational self-consistent field and…
We formulate a one-center non-orthogonal configuration interaction singles (1C-NOCIS) theory for the computation of core excited states of an initial singlet state with two unpaired electrons. This model, which we refer to as 1C-NOCIS…
We consider gradient descent and quasi-Newton algorithms to optimize the full configuration interaction (FCI) ground state wavefunction starting from an arbitrary reference state $|0 \rangle$. We show that the energies obtained along the…
Selected configuration interaction (sCI) methods including second-order perturbative corrections provide near full CI (FCI) quality energies with only a small fraction of the determinants of the FCI space. Here, we introduce both a…
We present a uniform analysis of biased stochastic gradient methods for minimizing convex, strongly convex, and non-convex composite objectives, and identify settings where bias is useful in stochastic gradient estimation. The framework we…
We recently showed that macroscopic nuclear spin ensembles prepared in coherent spin states can dramatically enhance the interaction rates of weakly interacting cosmic relics-such as dark matter and the cosmic neutrino background-through…