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Record W4399349707 · doi:10.1007/978-3-031-51443-2_8

Some “Special” Topics: (8.1) Solvation, (8.2) Singlet Diradicals, and (8.3) a Note on Heavy Atoms and Transition Metals

2024· book-chapter· en· W4399349707 on OpenAlex
Errol G. Lewars

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueComputational Chemistry · 2024
Typebook-chapter
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsTrent University
Fundersnot available
KeywordsSolvationSinglet stateTransition metalChemical physicsHeavy metalsMaterials scienceChemistryAtomic physicsCondensed matter physicsPhysicsMoleculeEnvironmental chemistryOrganic chemistryCatalysisExcited state

Abstract

fetched live from OpenAlex

For some purposes solution-phase computations are necessary, e.g., for understanding certain reactions, and for the accurate prediction of p K a in solution. For introducing the effects of solvation there are two methodologies (and hybrids of these two): microsolvation or explicit solvation, and continuum solvation. Some molecular species are not calculated properly by straightforward model chemistries: these include singlet diradicals and some excited state species. For these the standard method is the complete active space approach, CAS (CASSCF, complete active space SCF). This is a limited version of configuration interaction, in which electrons are promoted from and to a carefully chosen set of molecular orbitals. For systems with heavy atoms we often employ pseudopotential basis sets (frequently relativistic), which reduce the computational burden of large numbers of electrons. Transition metals present problems beyond those of main-group heavy atoms: not only can relativistic effects be significant, but electron d- or f-levels, variably perturbed by ligands, make possible several electronic states. Also, nearly degenerate s and d levels can cause convergence problems. DFT calculations, with pseudopotentials, are the standard approach for computation on such compounds.

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.

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Theoretical or conceptual · Consensus signal: Theoretical or conceptual
GenreCandidate signal: Other · Consensus signal: none
Teacher disagreement score0.566
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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 head0.240
Teacher spread0.229 · 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