Exploiting the “Lego brick” approach to predict accurate molecular structures of PAHs and PANHs

Ye, Hexu; Alessandrini, Silvia; Melosso, Mattia; Puzzarini, Cristina

doi:10.1039/d2cp03294e

Cited by 15 publications

(52 citation statements)

References 58 publications

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“…On average, the deviation from experiment of the double-hybrid rev-DSDPBEP86 functional 64 is 0.4%, which reduces to about 0.1% when only the TM approach is applied. A further improvement, with a MAE of about 0.05%, is noted when moving to the complete TM+LR model 53 . Overall, the results of ref.…”

Section: How To Meet the Target Accuracymentioning

confidence: 92%

“…Overall, the results of ref. 53 demonstrate that the "Lego-brick" approach is robust, can be extended to systems of increasing size and is able to deal some degree flexibility.…”

Section: How To Meet the Target Accuracymentioning

confidence: 97%

“…been defined 7,10 . However, for systems, alternatives to brute-force computation, such as the locality-exploiting "Legobrick" approach [50][51][52][53] , are likely to prove more valuable in the future.…”

Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 99%

“…This model is based on the assumption that a molecular system can be seen as formed by smaller fragments for which a very accurate equilibrium structure is available and that the difference between the latter and the DFT determination can be directly applied to the larger system. Recently, this model has been extended to define the so-called "Lego-brick" approach (also denoted TM+LR or TM+LR_SE) 51,53 . Within this protocol, semi-experimental equilibrium structures are employed for the geometries of the fragments, the TM approach is exploited to account for the modifications occurring when going from the isolated fragment to the molecular system under investigation, and the "linear regression" (LR) model 78 is used to correct the linkage between different fragments.…”

Section: How To Meet the Target Accuracymentioning

confidence: 99%

“…In this context, for medium-sized molecules, reduced-cost composite schemes have been defined. 7,10 However, for larger systems, alternatives to bruteforce computation, such as the locality-exploiting ''Lego-brick'' approach, [50][51][52][53] are likely to prove more valuable in the future.…”

Section: Review Pccpmentioning

confidence: 99%

See 4 more Smart Citations

Connections between the accuracy of rotational constants and equilibrium molecular structures

Puzzarini

Stanton

2023

Phys. Chem. Chem. Phys.

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Section: How To Meet the Target Accuracymentioning

confidence: 92%

“…Overall, the results of ref. 53 demonstrate that the "Lego-brick" approach is robust, can be extended to systems of increasing size and is able to deal some degree flexibility.…”

Section: How To Meet the Target Accuracymentioning

confidence: 97%

Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 99%

Section: How To Meet the Target Accuracymentioning

confidence: 99%

Section: Review Pccpmentioning

confidence: 99%

See 3 more Smart Citations

Connections between the accuracy of rotational constants and equilibrium molecular structures

Puzzarini

Stanton

2023

Phys. Chem. Chem. Phys.

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Bringing Machine‐Learning Enhanced Quantum Chemistry and Microwave Spectroscopy to Conformational Landscape Exploration: the Paradigmatic Case of 4‐Fluoro‐Threonine

Barone

Fusè

Aguado

et al. 2023

Chemistry A European J

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A combined experimental and theoretical study has been carried out on 4‐fluoro‐threonine, the only naturally occurring fluorinated amino acid. Fluorination of the methyl group significantly increases the conformational complexity with respect to the parent amino acid threonine. The conformational landscape has been characterized in great detail, with special attention given to the inter‐conversion pathways between different conformers. This led to the identification of 13 stable low‐energy minima. The equilibrium population of so many conformers produces a very complicated and congested rotational spectrum that could be assigned through a strategy that combines several levels of quantum chemical calculations with the principles of machine learning. Twelve conformers out of 13 could be experimentally characterized. The results obtained from the analysis of the intra‐molecular interactions can be exploited to accurately model fluorine‐substitution effects in biomolecules.

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On the performance of composite schemes in determining equilibrium molecular structures

Sahoo,

Franke,

Stanton

2024

J Comput Chem

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Determination of equilibrium molecular structures is an essential ingredient in predicting spectroscopic parameters that help in identifying molecular carriers of microwave transitions. Here, the performance of two different ab initio composite approaches for obtaining equilibrium structures, “energy scheme” and “geometry scheme,” is explored and compared to semi‐experimental equilibrium structures. This study is performed for a set of 11 molecules which includes diatomics, linear triatomics, and a few non‐linear molecules. The ab initio calculations were performed using three tiers of composite chemical recipes. The current results show that as the overall rigor of calculation is increased, the semi‐experimental and the ab initio numbers agree to within 0.0003 Å for all molecules in the test set. The composite approach based on correcting the potential energy surface (energy scheme) and the one based on correcting the geometry directly (geometry scheme) show excellent agreement with each other. This work represents a step toward development of efficient and highly accurate procedures for computing ab initio equilibrium structures.

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Exploiting the “Lego brick” approach to predict accurate molecular structures of PAHs and PANHs

Abstract: Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) are important and ubiquitous species in space. However, their accurate structural and spectroscopic characterization is often missing. To fill this...

Cited by 15 publications

References 58 publications

Connections between the accuracy of rotational constants and equilibrium molecular structures

Connections between the accuracy of rotational constants and equilibrium molecular structures

Bringing Machine‐Learning Enhanced Quantum Chemistry and Microwave Spectroscopy to Conformational Landscape Exploration: the Paradigmatic Case of 4‐Fluoro‐Threonine

On the performance of composite schemes in determining equilibrium molecular structures

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