arXiv subjects

Somayeh Ahmadkhani

Publications and source records attributed to Somayeh Ahmadkhani.

6 recordsLinked to original sources

arXiv2026

Efficient and reliable modeling of large $π$-electron systems with the Pariser--Parr--Pople Hamiltonian and pCCD-based methods

Model Hamiltonians offer a cost-effective way to capture the key physics of large $π$-conjugated systems. In this work, we combine the Pariser--Parr--Pople (PPP) model Hamiltonian with pair Coupled Cluster Doubles (pCCD)-based methods to study the excited-state electronic structures of polycyclic aromatic hydrocarbons (PAHs). The model Hamiltonian is implemented in the open-source PyBEST software package, which provides numerous pCCD-type models that have been shown to perform well for the electronic structure properties of large organic molecules when combined with quantum-chemical Hamiltonians and all-electron basis sets. Within the PPP model, we probe canonical Hartree--Fock and natural pCCD-optimized orbitals in predicting excited-state properties using the linear response formalism on top of pCCD. Their performance is compared with configuration-interaction-based methods and the conventional EOM-CCSD approach. Our study demonstrates that pCCD/PPP-based approaches are an efficient, cost-effective, and accurate framework to compute excited-state properties in large $π$-conjugated organic systems, such as extended PAHs or other systems relevant to organic electronics.

physics.chem-ph↗

arXiv2026

Simple and efficient computational strategies for calculating orbital energies and pair-orbital energies from pCCD-based methods

We introduce affordable computational strategies for calculating orbital and pair-orbital energies in atomic and molecular systems. Our methods are based on the pair Coupled Cluster Doubles (pCCD) ansatz and its orbital-optimized variant. The computed orbital and pair-orbital energies are then subsequently used to approximate ionization potentials (IPs), electron affinities (EAs), the resulting charge gaps, double ionization potentials (DIPs), and double electron affinities (DEAs). Our methodology builds on the standard Koopmans' theorem and refines it for a pCCD-based wave function. Furthermore, we incorporate pCCD electron correlation effects into the model utilizing canonical Hartree-Fock or natural pCCD-optimized orbitals. The latter represents a diagonal approximation to the (D)IP/D(EA) equation of motion pCCD models. We benchmarked our newly developed models against theoretical and available experimental data for selected atoms in various basis set sizes and a set of 24 organic acceptor molecules. Our numerical results show that the Koopmans' approach based on pCCD natural orbitals provides a balanced treatment of occupied and virtual orbital energies, resulting in reliable predictions of charge gaps at a low computational cost.

physics.chem-ph↗

arXiv2026

Efficient Coupled-Cluster Python Frameworks for Next-Generation GPUs: A Comparative Study of CuPy and PyTorch on the Hopper and Grace Hopper Architecture

In this work, we introduce new batching algorithms to effectively handle large contractions encountered in coupled-cluster singles and doubles (CCSD) implementations in Python on the Video Random Access Memory (VRAM) of graphical processing units (GPUs), thereby improving performance. Specifically, we benchmark the performance of the CuPy and PyTorch libraries on a single NVIDIA Hopper (H100) and the Grace Hopper (GH200) architectures. We begin by optimizing the particle-particle ladder bottleneck contraction in CCSD using an asymmetric and dynamic splitting recipe, and then move toward a generic tensor contraction protocol that enables tensor contractions to be performed almost exclusively on GPUs. We benchmark our new, fully generic GPU-accelerated coupled-cluster implementations for various molecular systems and basis-set sizes, using both the CuPy and PyTorch libraries. While PyTorch outperforms CuPy on H100 by approximately 20\%, both perform similarly on the GH200 architecture. Compared to our initial GPU implementation [J. Chem. Theory Comput. 2024, 20, 3, 1130--1142], we achieve a 10-fold speedup. In molecular CCSD calculations, we report additional speedups between 3 and 16 for a single CCSD iteration using Cholesky-decomposed electron repulsion integrals compared to our original GPU-CPU hybrid implementation.

physics.chem-ph↗

arXiv2026

Open quantum systems beyond equilibrium: Lindblad equation and path integral molecular dynamics

The Lindblad equation determines the time evolution of the density operator of open quantum systems. While valid for any system size, its use is, in practice, restricted to prototype/surrogate models with the aim of tackling specific aspects of the overall quantum complexity of a multi-atomic system. Path integral molecular dynamics (PIMD) instead provides static and dynamical quantum statistical averages of physical observables for systems in equilibrium composed of up to thousands of atoms over timescales up to nanoseconds, under the condition that short-time quantum coherence is not relevant for the properties of interest. PIMD relies on the well-established technique of molecular dynamics (MD) with its associated classical trajectories. However, it cannot describe a direct time evolution of a system and its convergence to a stationary state in situations out of equilibrium. In this work, we analyze the link between the Lindblad equation and PIMD; specifically, we will discuss how PIMD can actually be used to calculate the time evolution of ensemble-averaged physical observables and their convergence to a stationary state for situations out of equilibrium, bypassing the need of explicitly solving the Lindblad equation. Yet, at the same time, the Lindblad equation and PIMD are linked to one another through a formal relation of equivalence, which provides an argument for the consistency of PIMD results, namely the positivity of the density operator at any time. A numerical study of a prototype system, which is of interest in chemical physics, will be used to showcase the method.

quant-ph↗

arXiv2024

Linear Response pCCD-Based Methods: LR-pCCD and LR-pCCD+S Approaches for the Efficient and Reliable Modeling of Excited state Properties

In this work, we derive working equations for the Linear Response pair Coupled Cluster Doubles (LR-pCCD) ansatz and its extension to singles (S), LR-pCCD+S. These methods allow us to compute electronic excitation energies and transition dipole moments based on a pCCD reference function. We benchmark the LR-pCCD+S model against the {linear response} coupled-cluster singles and doubles method for modeling electronic spectra (excitation energies and transition dipole moments) of the BH, \ce{H2O}, \ce{H2CO}, and furan molecules. We also analyze the effect of orbital optimization within pCCD on the resulting LR-pCCD+S transition dipole moments {and oscillator strengths} and perform a statistical error analysis. We show that the LR-pCCD+S method can correctly reproduce the transition dipole moments features, thus representing a reliable and cost-effective alternative to standard, more expensive electronic structure methods for modeling electronic spectra of simple molecules. Specifically, the proposed models require only mean-field-like computational cost, while excited-state properties may approach the CCSD level of accuracy. Moreover, we demonstrate the capability of our model to simulate electronic transitions with non-negligible contributions of double excitations and the electronic spectra of polyenes of various chain lengths, for which standard electronic structure methods perform purely.

physics.chem-ph↗

arXiv2019

Superconducting proximity effect in flat band systems

We study theoretically proximity-induced superconductivity and its inverse effect in dice lattice flat band model by considering Josephson junction with an s-wave pairing in the superconducting leads. Using self-consistent tight-binding Bogoliubov-de Gennes method, we show that there is a critical value for chemical potential of the superconductors depending on paring interaction strength over which for undoped normal region the proximity effect is enhanced. Whereas if the superconductor chemical potential is less than the critical one the proximity effect decreases regardless of normal region doping and in the meanwhile, the pairing amplitude of superconducting region increases significantly. Furthermore, we unveil that the supercurrent passing through the junction is large (vanishingly small) when the superconductor chemical potential is smaller (larger) than the critical value which increases as a function of normal region chemical potential.

cond-mat.mes-hall↗