Search arXiv⌕ Search

arXiv · 2609.37166

Adaptive Expansions of the Optimized Effective Potential in Physically Motivated Response Spaces

Abstract

The optimized effective potential (OEP) method provides an exact framework for incorporating orbital-dependent exchange within Kohn-Sham (KS) density-functional theory (DFT). Its practical implementation requires representing the exchange-response potential in a suitable auxiliary space, yet conventional choices are not necessarily adapted to the physical structure of the OEP response. Here, we introduce a general response-space strategy in which physically motivated response functions from existing model exchange potentials are repurposed as adaptive auxiliary directions for the OEP equation. Specifically, response functions associated with the Becke-Johnson (BJ), R"as"anen-Pittalis-Proetto (RPP), Gritsenko-van Leeuwen-van Lenthe-Baerends (GLLB), Krieger-Li-Iafrate (KLI), and localized Hartree-Fock (LHF) constructions are incorporated into compact auxiliary spaces, while their coefficients are determined directly from the projected OEP equation rather than fixed by the underlying model potentials. This establishes a systematic connection between model exchange potentials and finite-basis OEP: model potentials provide physically informed response directions, while OEP determines their system-dependent amplitudes. The framework encompasses one- and multidimensional response spaces, including occupied-orbital and occupied-pair representations, without modifying the underlying OEP condition. We show that these physically adapted spaces capture the dominant spatial structures of the OEP exchange response with substantially fewer degrees of freedom than conventional auxiliary expansions. The proposed approach therefore provides a general route to compact, adaptive representations of exchange-only OEP potentials and a systematic framework for developing low-dimensional OEP approximations from physically motivated model response functions.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Gabriel Chirchir, Aditi Singh, Yan Lukashevich, Igor Sawicki, Bogumiła Jezierska, Subrata Jana, Szymon Śmiga. 2026-09-29. Adaptive Expansions of the Optimized Effective Potential in Physically Motivated Response Spaces. https://arxiv.org/abs/2609.37166

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

Nuclear quantum effects enhance diffusion in supercooled ammonia through accelerated pyramidal inversion

In liquid ammonia, an imbalance between available hydrogen-bond donor and acceptor sites limits water-like tetrahedral connectivity, leaving sparse and short-lived associations within a densely packed liquid. We ask whether quantum-sensitive local rearrangements can nevertheless contribute appreciably to diffusion in this weakly connected liquid. We compare classical and thermostatted ring polymer molecular dynamics from 170 to 250 K using an r$^2$SCAN-trained machine learning force field. Ammonia can change its molecular geometry as the nitrogen atom passes through the plane of the three hydrogen atoms, a motion known as pyramidal inversion. Nuclear quantum effects increase the inversion rate and reduce its apparent activation energy. Inversion events are accompanied by transient reductions in hydrogen-bond coordination and local density within the first solvation shell. Although nuclear quantum effects lower density and viscosity throughout the studied range, diffusion remains only weakly affected in the warmer liquid. The quantum enhancement of diffusion emerges below approximately 210 K and reaches 18% at 170 K, tracking the enhancement of cage escape. These observations support an inversion-assisted contribution to diffusion, in which a spatially localized, quantum-sensitive internal motion couples to cage relaxation without a persistent tetrahedral network.

physics.chem-ph↗

A Visual Understanding of Circular Dichroism Spectroscopy: The Case of Interacting Chromophores

Exciton coupling shapes the photophysical and chiroptical properties of molecular aggregates, but a microscopic, real-space understanding of how intermolecular interactions generate circular dichroism (CD) remains incomplete. Here, we computationally investigate the microscopic origins of CD in coupled molecular dimers to separate intermolecular (topological) from intramolecular (intrinsic) chirality. A combination of time-dependent density functional theory and transition chiral tensor (TCT) analysis provides a quantitative, visually intuitive framework showing how electronic coupling strength, intermolecular separation, and relative angular orientation govern chiroptical response. We find that pairs of individually achiral chromophores exhibit robust, topological chiroptical signals which give rise to the conventional Cotton effect, a standard interpretation of derivative features in circular dichroism spectra. We next establish that intrinsically chiral chromophores, on the other hand, disrupt the Cotton effect due to the competition between intrinsic chirality and topological chirality. This work establishes a foundation for interpreting exciton-coupled CD spectra in molecular aggregates, supramolecular assemblies, and nanostructures using the TCT approach, which offers an attractive tool for analyzing chiroptical responses in complex multi-chromophore systems relevant to emerging quantum technologies.

physics.chem-ph↗

An atom-based machine-learned dipole-moment model and application to conjugated systems

We introduce a method for predicting the dipole moments of molecular systems by systematically decomposing the total dipole moment into the sum of atomic contributions using the wavefunction from density-functional-theory calculations, and then use graph neutral networks to predict this effective atomic dipole moment from input atomic structure. It is demonstrated that the dipole moments and dielectric function can be accurately predicted even for complicated conjugated systems where the previous bond-based model [Phys. Rev. B 110, 165159] fails. The inference cost of our model scales linearly with the number of atoms and is about 3 times faster compared with Born-effective-charge-based schemes, but shows similar or better accuracy for dielectric function at terahertz range.

physics.chem-ph↗