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Record W2317324985 · doi:10.1021/ct5002335

Simulation of Liquid and Supercritical Hydrogen Sulfide and of Alkali Ions in the Pure and Aqueous Liquid

2014· article· en· W2317324985 on OpenAlexaff
Esam A. Orabi, Guillaume Lamoureux

Bibliographic record

VenueJournal of Chemical Theory and Computation · 2014
Typearticle
Languageen
FieldPhysics and Astronomy
TopicSpectroscopy and Quantum Chemical Studies
Canadian institutionsConcordia University
Fundersnot available
KeywordsSupercritical fluidSolvationPolarizabilityChemistryWater modelAqueous solutionMoleculeSolvation shellAlkali metalThermodynamicsPhysical chemistryMolecular dynamicsComputational chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

A polarizable model for hydrogen sulfide (H2S) is optimized based on the experimental properties of the monomer and of the bulk liquid. The model is characterized by rigid SH bonds but flexible HSH angle and the polarizability is based on the Drude oscillator model. Bonded parameters and atomic charges are based on the experimental properties of the gaseous monomer. Atomic Lennard-Jones (LJ) parameters are adjusted based on the density of H2S around the critical point (in the temperature range 363-393 K and pressure range 8.023-10.013 MPa). The model gives binding energies for H2S dimers, trimers, and tetramers in good agreement with ab initio MP2(full)/6-311++G(d,p) results. It shows a liquid structure in very good agreement with neutron diffraction data. The model also gives density, self-diffusion coefficient, heat of vaporization, and dielectric constant of liquid hydrogen sulfide at the normal boiling point in good agreement with experimental data. In addition, the model is transferable to high temperature and pressure conditions, as evidenced from simulations up to 542.2 K and 40 MPa. The model is used in combination with the SWM4-NDP water model, with LJ parameters between the S and O atoms adjusted to reproduce the experimental hydration free energy of H2S. Simulations suggest that, in its first solvation shell, a single H2O molecule is solvated by 10 H2S molecules while a single H2S molecule is solvated by 20.5 H2O molecules. Pair-specific LJ parameters between alkali ions (Li(+), Na(+), K(+), Rb(+), Cs(+)) and the S atom are adjusted to reproduce ab initio binding energies of the ion-H2S pairs at the CCSD(T) level. Simulations based on these parameters show that alkali ions have higher coordination numbers and lower solvation free energies in liquid H2S than in liquid water or liquid ammonia. The model is also used to investigate the preferential solvation of the ions in aqueous solutions with a 10% H2S mole fraction. Results show that the ions are preferentially solvated by water in their first solvation shell but have no significant selectivity to either ligands in their second shells.

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 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 categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.217
Threshold uncertainty score0.187

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 head0.009
GPT teacher head0.276
Teacher spread0.267 · 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 teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
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

Citations20
Published2014
Admission routes1
Has abstractyes

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