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Record W2062164330 · doi:10.1063/1.3139002

Two-dimensional infrared spectroscopy of a structured liquid: Neat formamide

2009· article· en· W2062164330 on OpenAlexfundno aff
Manuela Lima, Riccardo Chelli, Victor V. Volkov, Roberto Righini

Bibliographic record

VenueThe Journal of Chemical Physics · 2009
Typearticle
Languageen
FieldPhysics and Astronomy
TopicSpectroscopy and Quantum Chemical Studies
Canadian institutionsnot available
FundersUniversità degli Studi di PerugiaUniversità di BolognaUniversity of TorontoRijksuniversiteit GroningenEnte Cassa di Risparmio di FirenzeUniversity of Pennsylvania
KeywordsFormamideAnharmonicityChemistryExcited stateRelaxation (psychology)Molecular physicsSpectroscopyInfrared spectroscopySpectral lineAb initioMolecular dynamicsInfraredDipoleMolecular vibrationMotional narrowingTwo-dimensional infrared spectroscopyChemical physicsAtomic physicsComputational chemistryMoleculeCondensed matter physicsPhysicsOpticsQuantum mechanics

Abstract

fetched live from OpenAlex

Vibrational dynamics of liquid formamide is studied in the spectral region of the amide I mode by means of linear and two-dimensional infrared spectroscopies. The two-dimensional spectrum has a complex structure to be connected to the partially excitonic nature of the vibrational states. The measurements performed on a 1:10 (12)C:(13)C formamide isotopic mixture allow separating the broadening contribution due to the inhomogeneous frequency distribution of the local oscillators from that of excitonic origin. A model based on the Kubo picture of the line broadening is used, together with the dynamic information obtained from a molecular dynamics simulation, to fit the spectra of the (12)C formamide impurity in the isotopic mixture. The relevant dynamical information, such as the amplitude of the frequency fluctuations, lifetime of the second vibrational excited state, and anharmonicity, is thus recovered. By appropriately combining the outcomes of experiments and molecular dynamics simulation, we demonstrate that motional narrowing determines the line shape of the amide I resonance to a large extent. The same analysis provides an estimate of the transition dipole moment of formamide, which results in good agreement with an ab initio calculation. The calculated frequency fluctuation correlation time is found to be comparable to the hydrogen-bond lifetime, which defines the basic structural relaxation rate of the networked liquid.

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)0.000
metaresearch head score (Gemma)0.000
Version: metacan-v3-hybrid-931329e0061cValidation 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 score0.001
Threshold uncertainty score0.003

Distilled classifier scores by category (both heads)

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)0.0010.000

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 head0.008
GPT teacher head0.260
Teacher spread0.252 · 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 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

Citations13
Published2009
Admission routes1
Has abstractyes

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