arXiv subjects

Katharina Boguslawski

Publications and source records attributed to Katharina Boguslawski.

At least 19 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

Ionization Potentials at Mean-Field Computational Cost: The Extended Koopmans' Framework for pCCD

We introduce a mean-field-like computational model for calculating ionization potentials (IPs) based on the pair Coupled Cluster Doubles (pCCD) wave function. Specifically, our model combines the extended Koopmans' theorem (EKT) with the advantages of a variationally orbital-optimized (oo)-pCCD ansatz. The computational cost of the EKT(pCCD) method is negligible (O(N^3)) as the response 1- and 2-particle reduced density matrices used to construct the generalized Fock matrix are readily available after an oo-pCCD calculation. We benchmarked our new computational model for IPs of atoms, small molecules, and a set of organic acceptor molecules against experimental and theoretical reference data. The EKT(pCCD) model significantly improves upon the modified Koopmans' approach [J. Chem. Phys. 162, 184110 (2025)], and the obtained IPs are comparable to those of computationally more expensive IP-EOM-pCCD-based models, approaching CCSD(T) reference values (with a mean error of 0.05 eV). Most importantly, the EKT(pCCD) approach is almost independent of the basis set size, and reliable IPs are already obtained with small basis sets.

physics.chem-ph↗

arXiv2026

Analytic Gradients and Geometry Optimization for Orbital-Optimized Pair Coupled Cluster Doubles

We introduce a reusable geometry-optimization engine in PyBEST for analytic, gradient-driven molecular structure optimization, with particular emphasis on orbital-optimized pair coupled-cluster doubles (OOpCCD/AP1roG). The engine interfaces PyBEST with the \texttt{geomeTRIC} optimizer, combining analytic electronic-structure gradients from PyBEST with the translation-rotation-internal coordinate (TRIC) framework, step control, and convergence machinery provided by \texttt{geomeTRIC}. Specifically, we present the first implementation of analytic OOpCCD nuclear gradients within a Lagrangian formalism. Our approach and implementation are generally applicable to any seniority-zero wavefunctions that feature orbital optimization and allow for the evaluation of response one- and two-particle reduced density matrices. Owing to the seniority-zero structure of pCCD and the orbital stationarity of the optimized reference, the resulting gradient equations are compact, minimizing the storage of the full two-particle reduced density matrix, and avoiding finite-difference differentiation of wavefunction parameters. Validation on representative closed-shell systems shows that the OOpCCD-based PyBEST-\texttt{geomeTRIC} workflow converges robustly and reproduces reference equilibrium geometries and energies within tight tolerances. Most importantly, OOpCCD produces structural parameters that deviate by approximately 0.02 Å (0.01 Å) for bond lengths or less than 1$^\circ$ for bond angles from CCSD(F12c)(T*) (MP2) reference structures.

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

Oscillator Strengths and Transition Dipole Moments from a Simplified Equation-of-Motion Coupled Cluster Formalism within the Frozen-Pair Approximation

In this work, we derive the working equations for the transition density matrices within the equation-of-motion frozen-pair coupled-cluster framework. We focus specifically on the recently developed EOM-fpCCSD and EOM-ptCCSD models and present the corresponding transition dipole moments and oscillator strengths obtained via approximate expressions. This formulation avoids the computational overhead of solving the coupled-cluster $Λ$ equations. Furthermore, we employ a matrix inverse approximation to eliminate the need for explicit calculation of the left EOM eigenvectors. The accuracy of the resulting EOM-fpCCD and EOM-ptCCSD excited-state properties is benchmarked against the linear-response (LR)-CCSD method. Our results demonstrate that the description of excited state properties is improved when using EOM-fpCCSD and EOM-ptCCSD models compared to the standard EOM-CCSD variant.

physics.chem-ph↗

arXiv2026

Tuning Domain-Based Charge Transfer in Organic Dyes: Impact of Heteroatom Doping on the $π$-Linker of Carbazole-Based Systems

This work presents an innovative computational study of domain-based charge transfer that leverages the localized orbitals of pair coupled cluster doubles (pCCD). This method enables both directional monitoring and quantitative assessment of charge transfer among donor (D), bridge (B), and acceptor (A) moieties. We applied this approach to a series of newly designed carbazole-based prototypical organic dyes, doping the bridge at positions 1, 2, and 3 with nitrogen, oxygen, and sulfur atoms to generate mono-, di-, and tri-doped variants. Our results demonstrate a clear and progressive enhancement in charge transfer as the degree of nitrogen or oxygen doping increases from mono- to di- to tri-doped systems. For mono-doped dyes, the highest forward charge transfer from donor to bridge to acceptor (D$\xrightarrow{}$B$\xrightarrow{}$A) occurs when a heteroatom (N or O) is placed in the terminal ring of the bridge, closer to the acceptor. In di-doped dyes, the largest forward charge transfer is observed when heteroatoms occupy both terminal positions, with one atom (N or S) adjacent to the donor and the other (N) near the acceptor. Nitrogen-doped systems consistently outperform their oxygen and sulfur counterparts. Among all variants, the organic dye doped with three nitrogen atoms at the bridge exhibits the most efficient and highest directional donor-to-acceptor charge transfer (42.6%), making it the most promising candidate for potential applications in dye-sensitized solar cells. Finally, our calculations predict weak charge separation in all systems, indicating that charge transfer predominantly occurs from the bridge to the acceptor.

physics.chem-ph↗

arXiv2026

A Flexible, Automated, and Basis-Set Insensitive Domain-Based Charge-Transfer Decomposition for Correlated Wavefunctions and its Application to Inter- and Intramolecular Cases

We present a flexible, automated, and basis-set insensitive domain-based charge-transfer (CT) decomposition framework that can be combined with any CI-type excited-state wavefunction. Our approach is not based on excited-state densities and allows the excited-state character to be dissected into local and domain-based CT excitations and measures the individual contributions to each excited state. To guarantee a broad applicability, we introduce two domain-accumulation strategies to translate hole-particle substitutions to domain-domain excitations: a strict domain partitioning and a weighted approach suitable for small molecules and a large number of domains. The performance of both schemes is assessed for inter- and intramolecular CT excitations and various basis sets using EOM-CCSD and its simplified counterpart EOM-pCCD+S. Most importantly, the CT character is, to a large extent, basis-set independent, and both domain-accumulation schemes give consistent results. Overall, our framework provides a robust CT analysis and a domain resolution of the excitation character for a variety of computational setups and excited-state models.

physics.chem-ph↗

arXiv2026

EOM-fpCCSD: An Accurate Alternative to EOM-CCSD for Doubly Excited and Charge-Transfer States

We introduce a new equation-of-motion coupled-cluster method based on a pair coupled-cluster doubles (pCCD) reference, termed frozen-pair EOM-CCSD (EOM-fpCCSD). This approach combines the computational efficiency of the pCCD ansatz with a dynamical correlation correction, enabling a reliable description of electronically excited states within the EOM framework. The method has been implemented in the open-source PyBEST software package. Its performance is systematically benchmarked against standard EOM-CCSD and its pair-tailored variant (EOM-ptCCSD), using both canonical Hartree-Fock and pCCD natural orbitals. For charge-transfer (CT) excitations taken from the QUEST database, EOM-fpCCSD yields excitation energies very close to those of EOM-CCSD, outperforming EOM-ptCCSD, as well as to the theoretical best estimates (TBEs). Working within the localized pCCD natural orbital basis allows us to determine the directed CT character, which quantifies the directed charge flow from one molecular domain to another. Numerical results show that EOM-fpCCSD, EOM-CCSD, and EOM-ptCCSD provide nearly identical descriptions of the directed CT character, despite changes in excitation energies. The true advantage of EOM-fpCCSD becomes evident for the challenging QUEST subset of doubly excited states. While EOM-ptCCSD performs similarly to standard EOM-CCSD, EOM-fpCCSD significantly outperforms both methods for these problematic states compared to TBEs. In addition to improving the accuracy of excitation energies, EOM-fpCCSD also converges for several states that standard EOM-CCSD and EOM-ptCCSD fail to converge. These results demonstrate that EOM-fpCCSD offers a promising and computationally efficient route toward a more accurate description of complex electronic excitations.

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↗

arXiv2024

The relationship between structure and excited-state properties in polyanilines from geminal-based methods

We employ state-of-the-art quantum chemistry methods to study the structure-to-property relationship in polyanilines (PANIs) of different lengths and oxidation states. Specifically, we focus on leucoemeraldine, emeraldine, and pernigraniline in their tetramer and octamer forms. We scrutinize their structural properties, HOMO and LUMO energies, HOMO-LUMO gaps, and vibrational and electronic spectroscopy using various Density Functional Approximations (DFAs). Furthermore, the accuracy of DFAs is assessed by comparing them to experimental and wavefunction-based reference data. We perform large-scale orbital-optimized pair-Coupled Cluster Doubles (oo-pCCD) calculations for ground and electronically excited states and conventional Configuration Interaction Singles (CIS) calculations for electronically excited states in all investigated systems. The EOM-pCCD+S approach with pCCD-optimized orbitals allows us to unambiguously identify charge transfer and local transitions across the investigated PANI systems -- an analysis not possible within a delocalized canonical molecular orbital basis obtained, for instance, by DFAs. We show that the low-lying part of the emeraldine and pernigraniline spectrum is dominated by charge transfer excitations and that polymer elongation changes the character of the leading transitions. Furthermore, we augment our study with a quantum informational analysis of orbital correlations in various forms of PANIs.

physics.chem-ph↗

arXiv2024

Changing the paradigm in f-containing cold molecules: the impact of spin-orbit coupling and f-d transitions on quasi-bound vibrational states

Present-day state-of-the-art ab initio many-body calculations on f-block containing cold molecules heavily focus on perturbative approaches for spin-orbit coupling and exclude a substantial part of the atomic transitions in the $f$- and $d$-shell. Here, we demonstrate the cruciality of a proper relativistic treatment of the $f$- and $d$-shell in Yb-containing diatomics and the inclusion of $f\rightarrow d$ transitions to obtain physically sound elastic scatterings and pre-dissociation lifetimes. We focus on state-of-the-art relativistic many-body calculations for the Yb atom's ground- and excited-state and the YbLi$^+$ potential energy surface. For that purpose, we exploit various quantum many-body methods, namely a spin-free and four-component implementation of the coupled cluster singles and doubles (CCSD) model and its equation of motion extensions, spin-free complete active space self-consistent field, and internally contracted multi-reference (MR) configuration interaction approaches, and spin-free MRCCSD with a perturbative and full triples correction. We oppose scalar relativistic calculations to four-component variants to support the reliability of our EOM-CCSD study and shed new light on the interplay between these systems' spin-orbit coupling and the proper treatment of relativistic effects. Most importantly, we observe a significant shift in the electronic spectra of the $f\rightarrow d$ excitation block. We also provide new reference potential energy surfaces for ground and excited states for which theoretically sound elastic scattering and pre-dissociation lifetimes are calculated.

physics.atom-ph↗

arXiv2024

Delving into the Catalytic Mechanism of Molybdenum Cofactors: A Novel Coupled Cluster Study

In this work, we use modern electronic structure methods to model the catalytic mechanism of different variants of the molybdenum cofactor (Moco). We investigate the dependence of various Moco model systems on structural relaxation and the importance of environmental effects for five critical points along the reaction coordinate with the DMSO and NO$_3^-$ substrates. Furthermore, we scrutinize the performance of various coupled-cluster approaches for modeling the relative energies along the investigated reaction paths, focusing on several pair coupled cluster doubles (pCCD) flavors and conventional coupled cluster approximations. Moreover, we elucidate the Mo--O bond formation using orbital-based quantum information measures, which highlight the flow of $σ_{\rm M-O}$ bond formation and $σ_{\rm N/S-O}$ bond breaking. Our study shows that pCCD-based models are a viable alternative to conventional methods and offer us unique insights into the bonding situation along a reaction coordinate. Finally, this work highlights the importance of environmental effects or changes in the core and, consequently, in the model itself to elucidate the change in activity of different Moco variants.

physics.chem-ph↗

arXiv2024

Toward Reliable Dipole Moments without Single Excitations: The Role of Orbital Rotations and Dynamical Correlation

The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used to assess the accuracy and reliability of new electronic structure methods. This work analyses electronic dipole moments computed with the pair coupled cluster doubles (pCCD) ansatz and its linearized coupled cluster (pCCD-LCC) corrections using the canonical Hartree--Fock and pCCD-optimized (localized) orbital bases. The accuracy of pCCD-based dipole moments is assessed against experimental and CCSD(T) reference values using relaxed and unrelaxed density matrices and different basis set sizes. Our test set comprises molecules of various bonding patterns and electronic structures, exposing pCCD-based methods to a wide range of electron correlation effects. Additionally, we investigate the performance of pCCD-in-DFT dipole moments of some model complexes. Finally, our work indicates the importance of orbital relaxation in the pCCD model and shows the limitations of the linearized couple cluster corrections in predicting electronic dipole moments of multiple-bonded systems. Most importantly, pCCD with a linearized CCD correction can reproduce the dipole moment surfaces in singly-bonded molecules, which are comparable to the multi-reference ones.

physics.chem-ph↗

arXiv2024

Benchmarking ionization potentials from pCCD tailored coupled cluster models

The ionization potential (IP) is an important parameter providing essential insights into the reactivity of chemical systems. IPs are also crucial for designing, optimizing, and understanding the functionality of modern technological devices. We recently showed that limiting the CC ansatz to the seniority-zero sector proves insufficient in predicting reliable and accurate ionization potentials within an IP equation-of-motion coupled-cluster formalism. Specifically, the absence of dynamic correlation in the seniority-zero pair coupled cluster doubles (pCCD) model led to unacceptably significant errors of approximately 1.5 eV. In this work, we aim to explore the impact of dynamical correlation and the choice of the molecular orbital basis (canonical vs. localized) in CC-type methods targeting 201 ionized states in 41 molecules. We focus on pCCD-based approaches as well as the conventional IP-EOM-CCD and IP-EOM-CCSD. Their performance is compared to the CCSDT equivalent and experimental reference data. Our statistical analysis reveals that all investigated frozen-pair coupled cluster methods exhibit similar performance, with differences in errors typically within chemical accuracy (1 kcal/mol or 0.05 eV). Notably, the effect of the molecular orbital basis, such as canonical Hartree-Fock or natural pCCD-optimized orbitals, on the IPs is marginal if dynamical correlation is accounted for. Our study suggests that triple excitations are crucial in achieving chemical accuracy in IPs when modeling electron detachment processes with pCCD-based methods.

physics.chem-ph↗

arXiv2023

Accelerating Pythonic coupled cluster implementations: a comparison between CPUs and GPUs

We scrutinize how to accelerate the bottleneck operations of Pythonic coupled cluster implementations performed on a \texttt{NVIDIA} Tesla V100S PCIe 32GB (rev 1a) Graphics Processing Unit (GPU). The \texttt{NVIDIA} Compute Unified Device Architecture (CUDA) API is interacted with via \texttt{CuPy}, an open-source library for Python, designed as a \texttt{NumPy} drop-in replacement for GPUs. The implementation uses the Cholesky linear algebra domain and is done in {PyBEST}, the Pythonic Black-box Electronic Structure Tool -- a fully-fledged modern electronic structure software package. Due to the limitations of Video Memory (VRAM), the GPU calculations must be performed batch-wise. Timing results of some contractions containing large tensors are presented. The \texttt{CuPy} implementation leads to factor 10 speed-up compared to calculations on 36 CPUs. Furthermore, we benchmark several Pythonic routines for time and memory requirements to identify the optimal choice of the tensor contraction operations available. Finally, we compare an example CCSD and pCCD-LCCSD calculation performed solely on CPUs to their CPU--GPU hybrid implementation. Our results indicate a significant speed-up (up to a factor of 16 regarding the bottleneck operations) when offloading specific contractions to the GPU using \texttt{CuPy}.

physics.chem-ph↗

arXiv2023

Geminal-based strategies for modeling large building blocks of organic electronic materials

We elaborate on unconventional electronic structure methods based on geminals and their potential to advance the rapidly developing field of organic photovoltaics (OPV). Specifically, we focus on the computational advantages of geminal-based methods over standard approaches and identify the critical aspects of OPV development. Examples are reliable and efficient computations of orbital energies, electronic spectra, and van-der-Waals interactions. Geminal-based models can also be combined with quantum embedding techniques and a quantum information analysis of orbital interactions to gain a fundamental understanding of the electronic structures and properties of realistic OPV building blocks. Furthermore, other organic components present in, for instance, dye-sensitized solar cells (DSSC) represent another promising scope of application. Finally, we provide numerical examples predicting the properties of a small building block of OPV components and two carbazole-based dyes proposed as possible DSSC sensitizers.

physics.chem-ph↗

arXiv2023

Static Embedding with Pair Coupled Cluster Doubles Based Methods

Quantum embedding methods have recently developed significantly to model large molecular structures. This work proposes a novel wave function theory in density functional theory (WTF-in-DFT) embedding scheme based on pair-coupled cluster doubles (pCCD)-type methods. While pCCD can reliably describe strongly-correlated systems with mean-field-like computational cost, the large extent of dynamic correlation can be accounted for by (linearized) coupled-cluster corrections on top of the pCCD wave function. Here we focus on the linearized coupled-cluster singles and doubles (LCCSD) ansatz for electronic ground states and its extension to excited states within the equation of motion (EOM) formalism. We test our EOM-pCCD-LCCSD-in-DFT approach for the vertical excitation energies of the hydrogen-bonded water--ammonia complex and uranyl tetrahalides (UO$_2$X$_4^{2-}$, X=F, Cl, Br). Furthermore, we assess the quality of the embedding potential using an orbital entanglement and correlation analysis. The approximate models successfully capture changes in the excitation energies going from bare fragments to supramolecular structures and represent a promising computation model for excited states in large molecular systems.

physics.chem-ph↗

arXiv2023

Benchmarking ionization potentials from the simple pCCD model

The electron-detachment energy is measured by its ionization potential (IP). As a result, it is a fundamental observable and important molecular electronic signature in photoelectron spectroscopy. A precise theoretical prediction of electron-detachment energies or ionization potentials is essential for organic optoelectronic systems like transistors, solar cells, or light-emitting diodes. In this work, we benchmark the performance of the recently presented IP variant of the equation-of-motion pair coupled cluster doubles (IP-EOM-pCCD) model to determine IPs. Specifically, the predicted ionization energies are compared to experimental results and higher-order coupled cluster theories based on statistically assessing 201 electron-detached states of 41 organic molecules for three different molecular orbital basis sets and two sets of particle-hole operators. While IP-EOM-pCCD features a reasonable spread and skewness of ionization energies, its mean error and standard deviation deviate up to 1.5 eV from reference data. Our study, thus, highlights the importance of dynamical correlation to reliably predict IPs from a pCCD reference function in small organic molecules.

physics.chem-ph↗