Performant automatic differentiation of local coupled cluster theories: Response properties and ab initio molecular dynamics.

In this work, we introduce a differentiable implementation of the local natural orbital coupled cluster (LNO-CC) method within the automatic differentiation framework of the PySCFAD package. The implementation is comprehensively tuned for enhanced performance, which enables the calculation of first-order static response properties on medium-sized molecular systems using coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. We evaluate the accuracy of our method by benchmarking it against the canonical CCSD(T) reference for nuclear gradients, dipole moments, and geometry optimizations. In addition, we demonstrate the possibility of property calculations for chemically interesting systems through the computation of bond orders and Mössbauer spectroscopy parameters for a [NiFe]-hydrogenase active site model, along with the simulation of infrared spectra via ab initio LNO-CC molecular dynamics for a protonated water hexamer.

Converting Commodity Polyolefins to Electronic Materials through Borane-Catalyzed Alkene Isomerization.

Novel approaches to the functionalization of commodity polymers could provide avenues for the synthesis of materials for next-generation electronic devices. Herein, we present a catalytic method for the conversion of common unsaturated polymers such as polybutadiene, polyisoprene, and styrene-butadiene copolymers [e.g., polystyrene-block-polybutadiene-block-polystyrene and poly(styrene-stat-butadiene)] to poly(acetylene) (PA)-based multiblock copolymers with conjugation lengths of up to ∼20, making them potentially suitable for electronics applications. Additionally, we demonstrate the application of this method to the formal conversion of polyethylene─the most widely produced thermoplastic─into PA-containing multiblock materials.

Diabatic Valence-Hole States in the C2 Molecule: "Putting Humpty Dumpty Together Again".

Despite the long history of spectroscopic studies of the C2 molecule, fundamental questions about its chemical bonding are still being hotly debated. The complex electronic structure of C2 is a consequence of its dense manifold of near-degenerate, low-lying electronic states. A global multi-state diabatic model is proposed here to disentangle the numerous configuration interactions that occur within four symmetry manifolds of excited states of C2 (1Πg, 3Πg, 1Σu+ , and 3Σu+ ). The key concept of our model is the existence of two "valence-hole" configurations, 2σg22σu11πu33σg2 for 1,3Πg states and 2σg22σu11πu43σg1 for 1,3Σu+ states, that are derived from 3σg ← 2σu electron promotion. The lowest-energy state from each of the four C2 symmetry species is dominated by this type of valence-hole configuration at its equilibrium internuclear separation. As a result of their large binding energy (nominal bond order of 3) and correlation with the 2s22p2 + 2s2p3 separated-atom configurations, the presence of these valence-hole configurations has a profound impact on the global electronic structure and unimolecular dynamics of C2.

Accurate thermochemistry of covalent and ionic solids from spin-component-scaled MP2.

We study the performance of spin-component-scaled second-order Møller-Plesset perturbation theory (SCS-MP2) for the prediction of the lattice constant, bulk modulus, and cohesive energy of 12 simple, three-dimensional covalent and ionic semiconductors and insulators. We find that SCS-MP2 and the simpler scaled opposite-spin MP2 (SOS-MP2) yield predictions that are significantly improved over the already good performance of MP2. Specifically, when compared to experimental values with zero-point vibrational corrections, SCS-MP2 (SOS-MP2) yields mean absolute errors of 0.015 (0.017) Å for the lattice constant, 3.8 (3.7) GPa for the bulk modulus, and 0.06 (0.08) eV for the cohesive energy, which are smaller than those of leading density functionals by about a factor of two or more. We consider a reparameterization of the spin-scaling parameters and find that the optimal parameters for these solids are very similar to those already in common use in molecular quantum chemistry, suggesting good transferability and reliable future applications to surface chemistry on insulators.

Tight distance-dependent estimators for screening two-center and three-center short-range Coulomb integrals over Gaussian basis functions.

We derive distance-dependent estimators for two-center and three-center electron repulsion integrals over a short-range Coulomb potential, erfc(ωr12)/r12. These estimators are much tighter than the ones based on the Schwarz inequality and can be viewed as a complement to the distance-dependent estimators for four-center short-range Coulomb integrals and for two-center and three-center full Coulomb integrals previously reported. Because the short-range Coulomb potential is commonly used in solid-state calculations, including those with the Heyd-Scuseria-Ernzerhof functional and with our recently introduced range-separated periodic Gaussian density fitting, we test our estimators on a diverse set of periodic systems using a wide range of the range-separation parameter ω. These tests demonstrate the robust tightness of our estimators, which are then used with integral screening to calculate periodic three-center short-range Coulomb integrals with linear scaling in system size.

Fast periodic Gaussian density fitting by range separation.

We present an efficient implementation of periodic Gaussian density fitting (GDF) using the Coulomb metric. The three-center integrals are divided into two parts by range-separating the Coulomb kernel, with the short-range part evaluated in real space and the long-range part in reciprocal space. With a few algorithmic optimizations, we show that this new method-which we call range-separated GDF (RSGDF)-scales sublinearly to linearly with the number of k-points for small to medium-sized k-point meshes that are commonly used in periodic calculations with electron correlation. Numerical results on a few three-dimensional solids show about ten-fold speedups over the previously developed GDF with little precision loss. The error introduced by RSGDF is about 10-5Eh in the converged Hartree-Fock energy with default auxiliary basis sets and can be systematically reduced by increasing the size of the auxiliary basis with little extra work.

Bootstrap embedding with an unrestricted mean-field bath.

A suite of quantum embedding methods have recently been developed where the Schmidt decomposition is applied to the full system wavefunction to derive basis states that preserve the entanglement between the fragment and the bath. The quality of these methods can depend heavily on the quality of the initial full system wavefunction. Most of these methods, including bootstrap embedding (BE) [M. Welborn et al; J. Chem. Phys. 145, 074102 (2016)], start from a spin-restricted mean-field wavefunction [call this restricted BE (RBE)]. Given that spin-unrestricted wavefunctions can capture a significant amount of strong correlation at the mean-field level, we suspect that starting from a spin-unrestricted mean-field wavefunction will improve these embedding methods for strongly correlated systems. In this work, BE is generalized to an unrestricted Hartree-Fock bath [call this unrestricted BE (UBE)], and UBE is applied to model hydrogen ring systems. UBE's improved versatility over RBE is utilized to calculate high spin symmetry states that were previously unattainable with RBE. Ionization potentials, electron affinities, and spin-splittings are computed using UBE with accuracy on par with spin-unrestricted coupled cluster singles and doubles. Even for cases where RBE is viable, UBE converges more reliably. We discuss the limitations or weaknesses of each calculation and how improvements to RBE and density matrix embedding theory these past few years can also improve UBE.

An N-Heterocyclic-Carbene-Derived Distonic Radical Cation.

We present the discovery of a novel radical cation formed through one-electron oxidation of an N-heterocyclic carbene-carbodiimide (NHC-CDI) zwitterionic adduct. This compound possesses a distonic electronic structure (spatially separate spin and charge regions) and displays persistence under ambient conditions. We demonstrate its application in a redox-flow battery exhibiting minimal voltage hysteresis, a flat voltage plateau, high Coulombic efficiency, and no performance decay for at least 100 cycles. The chemical tunability of NHCs and CDIs suggests that this approach could provide a general entry to redox-active NHC-CDI adducts and their persistent radical ions for various applications.

Photoswitchable Sol-Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin-Decorated Cu24 L24 Metal-Organic Cages as Junctions.

Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu24 L24 metal-organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this "polyMOC" material can be reversibly switched between CuII , CuI , and Cu0 . The instability of the MOC junctions in the CuI and Cu0 states leads to network disassembly, forming CuI /Cu0 solutions, respectively, that are stable until re-oxidation to CuII and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.

Incremental embedding: A density matrix embedding scheme for molecules.

The idea of using fragment embedding to circumvent the high computational scaling of accurate electronic structure methods while retaining high accuracy has been a long-standing goal for quantum chemists. Traditional fragment embedding methods mainly focus on systems composed of weakly correlated parts and are insufficient when division across chemical bonds is unavoidable. Recently, density matrix embedding theory and other methods based on the Schmidt decomposition have emerged as a fresh approach to this problem. Despite their success on model systems, these methods can prove difficult for realistic systems because they rely on either a rigid, non-overlapping partition of the system or a specification of some special sites (i.e., "edge" and "center" sites), neither of which is well-defined in general for real molecules. In this work, we present a new Schmidt decomposition-based embedding scheme called incremental embedding that allows the combination of arbitrary overlapping fragments without the knowledge of edge sites. This method forms a convergent hierarchy in the sense that higher accuracy can be obtained by using fragments involving more sites. The computational scaling for the first few levels is lower than that of most correlated wave function methods. We present results for several small molecules in atom-centered Gaussian basis sets and demonstrate that incremental embedding converges quickly with fragment size and recovers most static correlation in small basis sets even when truncated at the second lowest level.

σ-SCF: A direct energy-targeting method to mean-field excited states.

The mean-field solutions of electronic excited states are much less accessible than ground state (e.g., Hartree-Fock) solutions. Energy-based optimization methods for excited states, like Δ-SCF (self-consistent field), tend to fall into the lowest solution consistent with a given symmetry-a problem known as "variational collapse." In this work, we combine the ideas of direct energy-targeting and variance-based optimization in order to describe excited states at the mean-field level. The resulting method, σ-SCF, has several advantages. First, it allows one to target any desired excited state by specifying a single parameter: a guess of the energy of that state. It can therefore, in principle, find all excited states. Second, it avoids variational collapse by using a variance-based, unconstrained local minimization. As a consequence, all states-ground or excited-are treated on an equal footing. Third, it provides an alternate approach to locate Δ-SCF solutions that are otherwise hardly accessible by the usual non-aufbau configuration initial guess. We present results for this new method for small atoms (He, Be) and molecules (H2, HF). We find that σ-SCF is very effective at locating excited states, including individual, high energy excitations within a dense manifold of excited states. Like all single determinant methods, σ-SCF shows prominent spin-symmetry breaking for open shell states and our results suggest that this method could be further improved with spin projection.

Monte-Carlo simulations of spin-crossover phenomena based on a vibronic Ising-like model with realistic parameters.

Materials with spin-crossover (SCO) properties hold great potential in information storage and therefore have received a lot of concerns in recent decades. The hysteresis phenomena accompanying SCO are attributed to the intermolecular cooperativity whose underlying mechanism may have a vibronic origin. In this work, a new vibronic Ising-like model in which the elastic coupling between SCO centers is included by considering harmonic stretching and bending (SAB) interactions is proposed and solved by Monte Carlo (MC) simulations. The key parameters in the new model, k1 and k2, corresponding to the elastic constant of the stretching and bending mode, respectively, can be directly related to the macroscopic bulk and shear modulus of the material of study, which can be readily estimated either based on experimental measurements or first-principles calculations. Using realistic parameters estimated based on density-functional theory calculations of a specific polymeric coordination SCO compound, [Fe(pz)Pt(CN)4]·2H2O (pz = pyrazine), temperature-induced hysteresis and pressure effects on SCO phenomena are simulated successfully. Our MC simulations shed light on the role of the vibronic couplings in the thermal hysteresis of SCO systems, and also point out the limitations of highly simplified Ising-like models for quantitative description of real SCO systems, which will be of great value for the development of more realistic SCO models.

Toward Linear Scaling Auxiliary-Field Quantum Monte Carlo with Local Natural Orbitals.

We develop a local correlation variant of auxiliary-field quantum Monte Carlo (AFQMC) based on local natural orbitals (LNO-AFQMC). In LNO-AFQMC, independent AFQMC calculations are performed for each localized occupied orbital using a truncated set of tailored orbitals. Because the size of this space does not grow with the system size for a target accuracy, the method has linear scaling. Applying LNO-AFQMC to molecular problems containing a few hundred to a thousand orbitals, we demonstrate convergence of total energies with significantly reduced costs. The savings are more significant for larger systems and larger basis sets. However, even for our smallest system studied, we find that LNO-AFQMC is cheaper than canonical AFQMC, in contrast with many other reduced-scaling methods. Perhaps most significantly, we show that energy differences converge much more quickly than total energies, making the method ideal for applications in chemistry and material science. Our work paves the way for linear scaling AFQMC calculations of strongly correlated systems, which would have a transformative effect on ab initio quantum chemistry.

Can Spin-Component Scaled MP2 Achieve kJ/mol Accuracy for Cohesive Energies of Molecular Crystals?

Attaining kJ/mol accuracy in cohesive energy for molecular crystals is a persistent challenge in computational materials science. In this study, we evaluate second-order Møller-Plesset perturbation theory (MP2) and its spin-component scaled models for calculating cohesive energies for 23 molecular crystals (X23 data set). Using periodic boundary conditions and Brillouin zone sampling, we converge results to the thermodynamic and complete basis set limits, achieving an accuracy of about 2 kJ/mol (0.5 kcal/mol), which is rarely achieved in previous MP2 calculations for molecular crystals. When compared to experimental data, our results have a mean absolute error of 12.9 kJ/mol, comparable to Density Functional Theory with the PBE functional and TS dispersion correction. By separately scaling the opposite-spin and same-spin correlation energy components, using predetermined parameters, we reduce the mean absolute error to 9.5 kJ/mol. Further fine-tuning of these scaling parameters specifically for the X23 data set brings the mean absolute error down to 7.5 kJ/mol.

Data-Efficient Machine Learning Potentials from Transfer Learning of Periodic Correlated Electronic Structure Methods: Liquid Water at AFQMC, CCSD, and CCSD(T) Accuracy.

Obtaining the atomistic structure and dynamics of disordered condensed-phase systems from first-principles remains one of the forefront challenges of chemical theory. Here we exploit recent advances in periodic electronic structure and provide a data-efficient approach to obtain machine-learned condensed-phase potential energy surfaces using AFQMC, CCSD, and CCSD(T) from a very small number (≤200) of energies by leveraging a transfer learning scheme starting from lower-tier electronic structure methods. We demonstrate the effectiveness of this approach for liquid water by performing both classical and path integral molecular dynamics simulations on these machine-learned potential energy surfaces. By doing this, we uncover the interplay of dynamical electron correlation and nuclear quantum effects across the entire liquid range of water while providing a general strategy for efficiently utilizing periodic correlated electronic structure methods to explore disordered condensed-phase systems.

Correlation-Consistent Gaussian Basis Sets for Solids Made Simple.

The rapidly growing interest in simulating condensed-phase materials using quantum chemistry methods calls for a library of high-quality Gaussian basis sets suitable for periodic calculations. Unfortunately, most standard Gaussian basis sets commonly used in molecular simulation show significant linear dependencies when used in close-packed solids, leading to severe numerical issues that hamper the convergence to the complete basis set (CBS) limit, especially in correlated calculations. In this work, we revisit Dunning's strategy for construction of correlation-consistent basis sets and examine the relationship between accuracy and numerical stability in periodic settings. We find that limiting the number of primitive functions avoids the appearance of problematic small exponents while still providing smooth convergence to the CBS limit. As an example, we generate double-, triple-, and quadruple-ζ correlation-consistent Gaussian basis sets for periodic calculations with Goedecker-Teter-Hutter (GTH) pseudopotentials. Our basis sets cover the main-group elements from the first three rows of the periodic table. Especially for atoms on the left side of the periodic table, our basis sets are less diffuse than those used in molecular calculations. We verify the fast and reliable convergence to the CBS limit in both Hartree-Fock and post-Hartree-Fock (MP2) calculations, using a diverse test set of 19 semiconductors and insulators.

Integral-Direct Hartree-Fock and Møller-Plesset Perturbation Theory for Periodic Systems with Density Fitting: Application to the Benzene Crystal.

We present an algorithm and implementation of integral-direct, density-fitted Hartree-Fock (HF) and second-order Møller-Plesset perturbation theory (MP2) for periodic systems. The new code eliminates the formerly prohibitive storage requirements and allows us to study systems 1 order of magnitude larger than before at the periodic MP2 level. We demonstrate the significance of the development by studying the benzene crystal in both the thermodynamic limit and the complete basis set limit, for which we predict an MP2 cohesive energy of -72.8 kJ/mol, which is about 10-15 kJ/mol larger in magnitude than all previously reported MP2 calculations. Compared to the best theoretical estimate from literature, several modified MP2 models approach chemical accuracy in the predicted cohesive energy of the benzene crystal and hence may be promising cost-effective choices for future applications on molecular crystals.

Ground-State Properties of Metallic Solids from Ab Initio Coupled-Cluster Theory.

Metallic solids are an enormously important class of materials, but they are a challenging target for accurate wave function-based electronic structure theories and have not been studied in great detail by such methods. Here, we use coupled-cluster theory with single and double excitations (CCSD) to study the structure of solid lithium and aluminum using optimized Gaussian basis sets. We calculate the equilibrium lattice constant, bulk modulus, and cohesive energy and compare them to experimental values, finding accuracy comparable to common density functionals. Because the quantum chemical "gold standard" CCSD(T) (CCSD with perturbative triple excitations) is inapplicable to metals in the thermodynamic limit, we test two approximate improvements to CCSD, which are found to improve the results.

Accurate Electronic Excitation Energies in Full-Valence Active Space via Bootstrap Embedding.

Fragment embedding has been widely used to circumvent the high computational scaling of using accurate electron correlation methods to describe the electronic ground states of molecules and materials. However, similar applications that utilize fragment embedding to treat electronic excited states are comparably less reported in the literature. The challenge here is twofold. First, most fragment embedding methods are most effective when the property of interest is local, but the change of the wave function upon excitation is nonlocal in general. Second, even for local excitations, an accurate estimate of, for example, the excitation energy can still be challenging owing to the need for a balanced treatment of both the ground and the excited states. In this work, we show that bootstrap embedding (BE), a fragment embedding method developed recently by our group, is promising toward describing general electronic excitations. Numerical simulations show that the excitation energies in full-valence active space (FVAS) can be well-estimated by BE to an error of ∼0.05 eV using relatively small fragments, for both local excitations and the excitations of some large dye molecules that exhibit strong charge-transfer characters. We hence anticipate BE to be a promising solution to accurately describing the excited states of large chemical systems.

Bootstrap Embedding For Large Molecular Systems.

Recent developments in quantum embedding theories have provided attractive approaches to correlated calculations for large systems. In this work, we extend our previous work [J. Chem. Theory Comput. 2019, 15, 4497-4506; J. Phys. Chem. Lett. 2019, 10, 6368-6374] on bootstrap embedding (BE) to enable correlated ab initio calculations at the coupled cluster with singles and doubles (CCSD) level for large molecules. We introduce several new algorithmic developments that significantly reduce the computational cost of BE, while maintaining its accuracy. The resulting implementation scales as O(N3) for the integral transform and O(N) for the CCSD calculation. Numerical results on a series of conjugated molecules suggest that BE with reasonably sized fragments can recover more than 99.5% of the total correlation energy of a full CCSD calculation, while the required computational resources (time and storage) compare favorably to one popular local correlation scheme: domain localized pair natural orbital (DLPNO). The largest BE calculation in this work involves ∼2900 basis functions and can be performed on a single node with 16 CPU cores and 64 GB of memory in a few days. We anticipate that these developments represent an important step toward the application of BE to solve practical problems.