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Diagonal perturbative triple corrections to the general‐model‐space state‐universal coupled‐cluster method: Are they warranted and useful?

2006· article· en· W2149821388 on OpenAlexaff
Xiangzhu Li, Josef Paldus

Bibliographic record

VenueMolecular Physics · 2006
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsUniversity of Waterloo
Fundersnot available
KeywordsCoupled clusterHamiltonian (control theory)Excited stateDiagonalExcitationPhysicsSpace (punctuation)Quantum mechanicsAtomic physicsMoleculeMathematicsGeometryComputer science

Abstract

fetched live from OpenAlex

The recently developed general‐model‐space (GMS) state‐universal (SU) coupled‐cluster (CC) approach, together with its version corrected for triples via a single‐reference (SR) CCSD(T)‐type correction of the diagonal elements of the effective Hamiltonian, is applied to several molecular electronic structure problems in order to assess their performance and the role of triples. These results are compared with an alternative handling of higher‐than‐pair clusters via the externally corrected SU CCSD method, denoted (M,N)‐CCSD, which employs N wave functions of the M‐reference CISD as an external source for N‐reference SU CCSD. These methods are applied to the problem of bond breaking in the ground and excited states of the F2 and HF molecules, where the high‐spin triplet component is also handled via the SR CCSD method. We further examine the vertical excitation energies of water and the basic spectroscopic constants (equilibrium geometries, harmonic frequencies, and excitation energies) for several low‐lying states of oxygen. The results are encouraging and are discussed from the viewpoint of the applicability and usefulness of perturbative‐type triple corrections.

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)0.006
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: none
GenreCandidate signal: Empirical · Consensus signal: none
Teacher disagreement score0.005
Threshold uncertainty score0.010

Distilled classifier scores by category (both heads)

CategoryCodexGemma
Metaresearch0.0010.006
Meta-epidemiology (narrow)0.0010.000
Meta-epidemiology (broad)0.0010.001
Bibliometrics0.0010.001
Science and technology studies0.0010.001
Scholarly communication0.0010.001
Open science0.0030.001
Research integrity0.0010.001
Insufficient payload (model declined to judge)0.0030.001

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 head0.008
GPT teacher head0.249
Teacher spread0.241 · 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

Citations12
Published2006
Admission routes1
Has abstractyes

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