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The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Quantum chemistry calculations of large, strongly correlated systems are typically limited by the computation cost that scales exponentially with the size of the system. Quantum algorithms, designed specifically for quantum computers, can alleviate this, but the resources required are still too large for today's quantum devices. Here, we present a quantum algorithm that combines a localization of multireference wave functions of chemical systems with quantum phase estimation (QPE) and variational unitary coupled cluster singles and doubles (UCCSD) to compute their ground-state energy. Our algorithm, termed "local active space unitary coupled cluster" (LAS-UCC), scales linearly with the system size for certain geometries, providing a polynomial reduction in the total number of gates compared with QPE, while providing accuracy above that of the variational quantum eigensolver using the UCCSD ansatz and also above that of the classical local active space self-consistent field. The accuracy of LAS-UCC is demonstrated by dissociating (H 2 ) 2 into two H 2 molecules and by breaking the two double bonds in trans -butadiene, and resource estimates are provided for linear chains of up to 20 H 2 molecules.

Multireference electronic structure methods, like the complete active space (CAS) self-consistent field model, have long been used to characterize chemically interesting processes. Important work has been done in recent years to develop modifications having a lower computational cost than CAS, but typically these methods offer no more chemical insight than that from the CAS solution being approximated. In this paper, we present the localized active space-state interaction (LASSI) method that can be used not only to lower the intrinsic cost of the multireference calculation but also to improve interpretability. The localized active space (LAS) approach utilizes the local nature of the electron-electron correlation to express a composite wave function as an antisymmetrized product of unentangled wave functions in local active subspaces. LASSI then uses these LAS states as a basis from which to express complete molecular wave functions. This not only makes the molecular wave function more compact but also permits flexibility in choosing those states to be included in the basis. Such selective inclusion of states translates to the selective inclusion of specific types of interactions, thereby allowing a quantitative analysis of these interactions. We demonstrate the use of LASSI to study charge migration and spin-flip excitations in multireference organic molecules. We also compute the J coupling parameter for a bimetallic compound using various LAS bases to construct the Hamiltonian to provide insights into the coupling mechanism.

Molecular electron spin qubits with optical manipulation schemes are some of the most promising candidates for modern quantum technologies. Key values that determine a compound's viability for optical-spin initialization and readout include its singlet-triplet gap and zero-field splitting (ZFS) parameters. Generally, these values are very small in magnitude and are thus difficult to reproduce with theoretical methods. Here, we study a previously identified optically addressable molecular qubit, (C 6 F 5 ) 3 trenVCN t Bu (tren = tris(2-aminoethyl)amine), using the complete active space self-consistent field (CASSCF) and post-CASSCF methods: complete active space second-order perturbation theory (CASPT2), multiconfiguration pair-density functional theory (MC-PDFT), and hybrid MC-PDFT (HMC-PDFT). Of those methods, we successfully reproduce the singlet-triplet gap and ZFS parameters with reasonable accuracy using 0.5 HMC-PDFT and CASPT2. Four additional V 3+ complexes with differing ligands were also investigated. We found that the ligands have minimal effect on the spin properties of the molecule and propose them to be optically addressable qubit candidates. These potential qubits are further analyzed in terms of ab initio ligand field theory (AILFT) to understand the influence of the ligands on the singlet-triplet gap and ZFS parameters.

Pseudotetrahedral organometallic complexes containing chromium(IV) and aryl ligands have been experimentally identified as promising molecular qubit candidates. Here we present a computational protocol based on multiconfiguration pair-density functional theory for computing singlet-triplet gaps and zero-field splitting (ZFS) parameters in Cr(IV) aryl complexes. We find that two multireference methods, multistate complete active space second-order perturbation theory (MS-CASPT2) and hybrid multistate pair-density functional theory (HMS-PDFT), perform better than Kohn-Sham density functional theory for singlet-triplet gaps. Despite the very small values of the ZFS parameters, both multireference methods performed qualitatively well. MS-CASPT2 and HMS-PDFT performed particularly well for predicting the trend in the ratio of the rhombic and axial ZFS parameters, | E / D |. We have also investigated the dependence and sensitivity of the calculated ZFS parameters on the active space and the molecular geometry. The methodologies outlined here can guide future prediction of ZFS parameters in molecular qubit candidates., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn-Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin-orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Accurate and affordable methods to characterize the electronic structure of solids are important for targeted materials design. Embedding-based methods provide an appealing balance in the trade-off between cost and accuracy─particularly when studying localized phenomena. Here, we use the density matrix embedding theory (DMET) algorithm to study the electronic excitations in solid-state defects with a restricted open-shell Hartree-Fock (ROHF) bath and multireference impurity solvers, specifically, complete active space self-consistent field (CASSCF) and n -electron valence state second-order perturbation theory (NEVPT2). We apply the method to investigate the electronic excitations in an oxygen vacancy (OV) on a MgO(100) surface and find absolute deviations within 0.05 eV between DMET using the CASSCF/NEVPT2 solver, denoted as CAS-DMET/NEVPT2-DMET, and the nonembedded CASSCF/NEVPT2 approach. Next, we establish the practicality of DMET by extending it to larger supercells for the OV defect and a neutral silicon vacancy in diamond where the use of nonembedded CASSCF/NEVPT2 is extremely expensive.

Accurate quantum chemical methods for the prediction of spin-state energy gaps for strongly correlated systems are computationally expensive and scale poorly with the size of the system. This makes calculations for many experimentally interesting molecules impractical even with abundant computational resources. Previous work has shown that the localized active space (LAS) self-consistent field (SCF) method can be an efficient way to obtain multiconfiguration SCF wave functions of comparable quality to the corresponding complete active space (CAS) ones. To obtain quantitative results, a post-SCF method is needed to estimate the complete correlation energy. One such method is multiconfiguration pair-density functional theory (PDFT), which calculates the energy based on the density and on-top pair density obtained from a multiconfiguration wave function. In this work, we introduce localized-active-space PDFT, which uses a LAS wave function for subsequent PDFT calculations. The method is tested by computing spin-state energies and gaps in conjugated organic molecules and a bimetallic compound and comparing to the corresponding CAS-PDFT values.

We propose a hybrid multiconfiguration pair-density functional theory (HMC-PDFT) that is a weighted average of complete-active-space self-consistent-field (CASSCF) and multiconfiguration pair-density functional theory (MC-PDFT) energies with a semiempirical parameter to control the fraction of CASSCF energy. We also explore a more general two-parameter hybrid method with a scaled correlation energy that allows us to compare to the recently proposed λ-MC-PDFT method. We scan the parameter space for the scaled-correlation method using test sets consisting of electronic excitation energies and diatomic bond energies, and we find no significant improvement by introducing the scaling parameter. We find that unscaled HMC-PDFT offers significantly improved accuracy over both CASSCF and the original MC-PDFT for a wide range of systems, and we present as an example of this approach "tPBE0", the "translated" MC-PDFT generalization of the popular PBE0 hybrid Kohn-Sham density functional.

Various metal oxide clusters upward of 8 atoms (Cu, Cd, Co, Fe, Ga, Mn, Mo, Ni, Sn, W, Zn, In, and Al) were incorporated into the pores of the metal-organic framework (MOF) NU-1000 via atomic layer deposition (ALD) and tested via high-throughput screening for catalytic isomerization and selective hydrogenation of propyne. Cu and Co were found to be the most active for propyne hydrogenation to propylene, and synergistic bimetallic combinations of Co and Zn, along with standalone Zn and Cd, were established as the most active for conversion to the isomerized product, propadiene. The combination of Co and Zn in NU-1000 diminished the propensity for full hydrogenation to propane as well as coking compared to its individual components. This study highlights the potential for high-throughput screening to survey monometallic and bimetallic cluster combinations that best affect the efficient transformation of small molecules, while discerning mechanistic differences in isomerization and hydrogenation by different metals.

Fragmentation methods applied to multireference wave functions constitute a road toward the application of highly accurate ab initio wave function calculations to large molecules and solids. However, it is important for reproducibility and transferability that a fragmentation scheme be well defined with minimal dependence on initial orbital guesses or user-designed ad hoc fragmentation schemes. One way to improve this sort of robustness is to ensure that the energy obeys a variational principle; that is, the active orbitals and active space wave functions minimize the electronic energy in a certain ansatz for the molecular wave function. We extended the theory of the localized active space self-consistent field, LASSCF, method ( JCTC 2019, 15, 972) to fully minimize the energy with respect to all orbital rotations, rendering it truly variational. The new method, called vLASSCF, substantially improves the robustness and reproducibility of the LAS wave function compared to LASSCF. We analyze the storage and operation cost scaling of vLASSCF compared to orbital optimization using a standard complete active space self-consistent field (CASSCF) approach, and we show results of vLASSCF calculations on some simple test systems. We show that vLASSCF is energetically equivalent to CASSCF in the limit of one active subspace and that vLASSCF significantly improves upon the reliability of LASSCF energy differences, allowing for more meaningful and subtle analysis of potential energy curves of dissociating molecules. We also show that all forms of LASSCF have a lower operation cost scaling than the orbital optimization part of CASSCF.

Quantitatively accurate calculations for spin-state ordering in transition-metal complexes typically demand a robust multiconfigurational treatment. The poor scaling of such methods with increasing size makes them impractical for large, strongly correlated systems. Density matrix embedding theory (DMET) is a fragmentation approach that can be used to specifically address this challenge. The single-determinantal bath framework of DMET is applicable in many situations, but it has been shown to perform poorly for molecules characterized by strong correlation when a multiconfigurational self-consistent field solver is used. To ameliorate this problem, the localized active space self-consistent field (LASSCF) method was recently described. In this work, LASSCF is applied to predict spin-state energetics in mono- and di-iron systems, and we show that the model offers an accuracy equivalent to that of CASSCF but at a substantially lower computational cost. Performance as a function of basis set and active space is also examined.