Global hybrid multiconfiguration pair-density functional theory

Mohammad Mostafanejad; Marcus Dante Liebenthal; A. Eugene DePrince III

Home/Archive/arXiv

arXiv · 1911.11162

Global hybrid multiconfiguration pair-density functional theory

Mohammad Mostafanejad·Marcus Dante Liebenthal·A. Eugene DePrince III

View original source ↗Read source document ↗Export metadata ↓

Abstract

A global hybrid extension of variational two-electron reduced-density matrix (v2RDM)-driven multiconfiguration pair-density functional theory (MCPDFT) is developed. Using a linear decomposition of the electron-electron repulsion term, a fraction λ of the nonlocal exchange interaction, obtained from v2RDM-driven complete active-space self-consistent field (CASSCF) theory, is combined with its local counterpart, obtained from an on-top pair-density functional. The resulting scheme (called λ-MCPDFT) inherits the benefits of MCPDFT (e.g., its simplicity and the resolution of the symmetry dilemma), and, when combined with the v2RDM approach to CASSCF, λ-MCPDFT requires only polynomially scaling computational effort. As a result, it can efficiently describe static and dynamical correlation effects in strongly correlated systems. The efficacy of the approach is assessed for several challenging multiconfigurational problems, including the dissociation of molecular nitrogen, the double dissociation of a water molecule, and the 1,3-dipolar cycloadditions of ozone to ethylene and ozone to acetylene in the O3ADD6 benchmark set.

Explore related subjects

physics.chem-ph

Keep this discovery

Explore connections, maps & timelines

BibTeX RIS

Mohammad Mostafanejad, Marcus Dante Liebenthal, A. Eugene DePrince III. 2019-11-25. Global hybrid multiconfiguration pair-density functional theory. https://arxiv.org/abs/1911.11162

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

KEEP EXPLORING

Related papers

arXiv2026

Intrinsic Matching Frustration in Fluctuating Finite Systems

We formulate intrinsic matching frustration (IMF), a fluctuation-induced, kinetics-independent reduction in the mean capacity permitted by a prescribed matching rule. For complementary one-to-one matching, the instantaneous capacity is set by the minority population, so fluctuations produce a nonzero mean deficit even when the two populations are balanced on average. At finite size, this deficit depends on the full distribution of the population difference and is determined by its variance alone only in the Gaussian limit. Compartmentalization hides matching capacity by preventing cancellation between local imbalances of opposite sign. Fusion releases this hidden capacity monotonically under coarse graining, producing a measurable recovery of product yield following local reaction to completion.

physics.chem-ph↗

arXiv2026

Phonon chirality as an additive control of CISS: a symmetry-protected law

Chirality-induced spin selectivity (CISS) is usually associated with molecular handedness. The possible contribution of chiral phonons is less established. We study a helical tight-binding model in which local phonon angular momentum modulates spin-dependent nearest-neighbor hopping. Fewest-switches surface hopping calculations give the transmitted spin polarization $\mathrm{SP}=aC+b\mathrm{PH}$. Here $C$ is the molecular chirality and $\mathrm{PH}$ is the phonon chirality. A mirror symmetry reverses $C$, $\mathrm{PH}$, and $\mathrm{SP}$ simultaneously. This symmetry excludes both a chirality-independent offset and a $C\cdot\mathrm{PH}$ term. The phonon contribution can therefore enhance, cancel, or reverse the molecular CISS signal.

physics.chem-ph↗

arXiv2026

A fast physics-based matrix model for the impedance of a PEM fuel cell: Incorporating functionally graded catalyst layer and channel impedances

We extend a recent physics-based matrix model for calculating PEM fuel cell impedance (doi:10.1149/2754-2734/ad6ce8) to cases of low air flow stoichiometry and functionally graded cathode catalyst layers (CCLs). We demonstrate that the matrix model produces accurate spectra and is almost three orders of magnitude faster than a model based on the standard boundary-value problem solver. The physics-based matrix model can compete with equivalent circuit models for fitting experimental EIS spectra, particularly those measured from cells with functionally graded CCL.

physics.chem-ph↗