State Preparation in Quantum Algorithms for Fragment-Based Quantum Chemistry.

State preparation for quantum algorithms is crucial for achieving high accuracy in quantum chemistry and competing with classical algorithms. The localized active space-unitary coupled cluster (LAS-UCC) algorithm iteratively loads a fragment-based multireference wave function onto a quantum computer. In this study, we compare two state preparation methods, quantum phase estimation (QPE) and direct initialization (DI), for each fragment. We test the two state preparation methods on three systems, ranging from a model system, a set of interacting hydrogen molecules, to more realistic chemical problems, like the C-C double bond breaking in transbutadiene and the spin ladder in a bimetallic system. We analyze the impact of QPE parameters, such as the number of ancilla qubits and Trotter steps, on the prepared state. We find a trade-off between the methods, where DI requires fewer resources for smaller fragments, while QPE is more efficient for larger fragments. Our resource estimates highlight the benefits of system fragmentation in state preparation for subsequent quantum chemical calculations. These findings have broad applications for preparing multireference quantum chemical wave functions on quantum circuits that can be used for realistic chemical applications.

Challenges in the Use of Quantum Computing Hardware-Efficient Ansätze in Electronic Structure Theory.

Advances in quantum computation for electronic structure, and particularly heuristic quantum algorithms, create an ongoing need to characterize the performance and limitations of these methods. Here we discuss some potential pitfalls connected with the use of hardware-efficient Ansätze in variational quantum simulations of electronic structure. We illustrate that hardware-efficient Ansätze may break Hamiltonian symmetries and yield nondifferentiable potential energy curves, in addition to the well-known difficulty of optimizing variational parameters. We discuss the interplay between these limitations by carrying out a comparative analysis of hardware-efficient Ansätze versus unitary coupled cluster and full configuration interaction, and of second- and first-quantization strategies to encode Fermionic degrees of freedom to qubits. Our analysis should be useful in understanding potential limitations and in identifying possible areas of improvement in hardware-efficient Ansätze.

Modeling Complex Solvent Effects on the Optical Rotation of Chiral Molecules: A Combined Molecular Dynamics and Density Functional Theory Study.

The challenge of assigning the absolute stereochemical configuration to a chiral compound can be overcome via accurate ab initio predictions of optical rotation, a sensitive molecular property that is further complicated by solvent effects. The solvent's "chiral imprint"-the transfer of the chirality from the solute to the surrounding achiral solvent-is explored here using conformational averaging and time-dependent density-functional theory. These complex solvent effects are taken into account via simple averaging over a molecular dynamics trajectory together with the explicit quantum mechanical consideration of the solvent molecules within the solute's cybotactic region and implicit modeling of the bulk solvent. We consider several axes along which the system's optical rotation varies, including the sampling of the dynamical trajectory, the quality of the one-electron basis set, and the use of continuum solvent models to account for bulk effects.

PNO++: Perturbed Pair Natural Orbitals for Coupled Cluster Linear Response Theory.

Reduced-scaling methods are needed to make accurate and systematically improvable coupled cluster linear response methods for the calculation of molecular properties tractable for large molecules. In this paper, we examine the perturbed pair natural orbital-based PNO++ approach that creates an orbital space optimized for response properties derived from a lower-cost field-perturbed density matrix. We analyze truncation errors in correlation energies, dynamic polarizabilities, and specific rotations from a coupled cluster singles and doubles (CCSD) reference. We find that incorporating a fixed number of orbitals from the pair natural orbital (PNO) space into the PNO++ method-a new method presented here, the "combined PNO++" approach-recovers accuracy in the CCSD correlation energy while preserving the well-behaved convergence behavior of the PNO++ method for linear response properties.

Machine-Learning Coupled Cluster Properties through a Density Tensor Representation.

The introduction of machine-learning (ML) algorithms to quantum mechanics enables rapid evaluation of otherwise intractable expressions at the cost of prior training on appropriate benchmarks. Many computational bottlenecks in the evaluation of accurate electronic structure theory could potentially benefit from the application of such models, from reducing the complexity of the underlying wave function parameter space to circumventing the complications of solving the electronic Schrödinger equation entirely. Applications of ML to electronic structure have thus far been focused on learning molecular properties (mainly the energy) from geometric representations. While this line of study has been quite successful, highly accurate models typically require a "big data" approach with thousands of training data points. Herein, we propose a general, systematically improvable scheme for wave function-based ML of arbitrary molecular properties, inspired by the underlying equations that govern the canonical approach to computing the properties. To this end, we combine the established ML machinery of the t-amplitude tensor representation with a new reduced density matrix representation. The resulting model provides quantitative accuracy in both the electronic energy and dipoles of small molecules using only a few dozen training points per system.

Dihydrochelerythrine and its derivatives: Synthesis and their application as potential G-quadruplex DNA stabilizing agents.

A convenient route was envisaged toward the synthesis of dihydrochelerythrine (DHCHL), 4 by intramolecular Suzuki coupling of 2-bromo-N-(2-bromobenzyl)-naphthalen-1-amine derivative 5 via in situ generated arylborane. This compound was converted to (±)-6-acetonyldihydrochelerythrine (ADC), 3 which was then resolved by chiral prep-HPLC. Efficiency of DHCHL for the stabilization of promoter quadruplex DNA structures and a comparison study with the parent natural alkaloid chelerythrine (CHL), 1 was performed. A thorough investigation was carried out to assess the quadruplex binding affinity by using various biophysical and biochemical studies and the binding mode was explained by using molecular modeling and dynamics studies. Results clearly indicate that DHCHL is a strong G-quadruplex stabilizer with affinity similar to that of the parent alkaloid CHL. Compounds ADC and DHCHL were also screened against different human cancer cell lines. Among the cancer cells, (±)-ADC and its enantiomers showed varied (15-48%) inhibition against human colorectal cell line HCT116 and breast cancer cell line MDA-MB-231 albeit low enantio-specificity in the inhibitory effect; whereas DHCHL showed 30% inhibition against A431 cell line only, suggesting the compounds are indeed cancer tissue specific.