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Record W2947265090 · doi:10.1063/1.5096405

An alternative derivation of orbital-free density functional theory

2019· article· en· W2947265090 on OpenAlexafffund
R. B. Thompson

Bibliographic record

VenueThe Journal of Chemical Physics · 2019
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsUniversity of Waterloo
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsDensity functional theoryPauli exclusion principleOrbital-free density functional theoryHamiltonian (control theory)Energy functionalTime-dependent density functional theoryStatistical physicsQuantum mechanicsMathematicsPhysicsMathematical optimization

Abstract

fetched live from OpenAlex

Polymer self-consistent field theory techniques are used to derive quantum density functional theory without the use of the theorems of density functional theory. Instead, a free energy is obtained from a partition function that is constructed directly from a Hamiltonian so that the results are, in principle, valid at finite temperatures. The main governing equations are found to be a set of modified diffusion equations, and the set of self-consistent equations are essentially identical to those of a ring polymer system. The equations are shown to be equivalent to Kohn-Sham density functional theory and to reduce to classical density functional theory, each under appropriate conditions. The obtained noninteracting kinetic energy functional is, in principle, exact but suffers from the usual orbital-free approximation of the Pauli exclusion principle in addition to the exchange-correlation approximation. The equations are solved using the spectral method of polymer self-consistent field theory, which allows the set of modified diffusion equations to be evaluated for the same computational cost as solving a single diffusion equation. A simple exchange-correlation functional is chosen, together with a shell-structure-based Pauli potential, in order to compare the ensemble average electron densities of several isolated atom systems to known literature results. The agreement is excellent, justifying the alternative formalism and numerical method. Some speculation is provided on considering the timelike parameter in the diffusion equations, which is related to temperature, as having dimensional significance, and thus picturing pointlike quantum particles instead as nonlocal, polymerlike, threads in a higher dimensional thermal-space. A consideration of the double-slit experiment from this point of view is speculated to provide results equivalent to the Copenhagen interpretation. Thus, the present formalism may be considered as a type of "pilot-wave," realist, perspective on density functional theory.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame machine prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.

metaresearch head score (Codex)0.001
metaresearch head score (Gemma)0.002
Version: metacan-v3-hybrid-931329e0061cValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Theoretical or conceptual · Consensus signal: Theoretical or conceptual
GenreCandidate signal: Empirical · Consensus signal: none
Teacher disagreement score0.007
Threshold uncertainty score0.024

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0010.002
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0010.002
Bibliometrics0.0020.002
Science and technology studies0.0010.001
Scholarly communication0.0020.002
Open science0.0030.001
Research integrity0.0020.002
Insufficient payload (model declined to judge)0.0070.002

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.011
GPT teacher head0.241
Teacher spread0.230 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designTheoretical or conceptual
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations10
Published2019
Admission routes2
Has abstractyes

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