Theoretical Approach to Evaluate the Gas-Sensing Performance of Graphene Nanoribbon/Oligothiophene Composites

Ashraf, Ayesha; Herbert, John M.; Muhammad, Shabbir; Farooqi, Bilal Ahmad; Farooq, Umar; Salman, Muhammad; Ayub, Khurshid

doi:10.1021/acsomega.1c05863

Cited by 12 publications

(8 citation statements)

References 83 publications

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“…In this section, we examine much larger molecular systems in order to understand how the magnitude of BSSE grows with system size. Systems examined include a set of layered complexes of oligothiophenes and graphene nanoribbons, , such as the example shown in Figure a. These range in size from 134 to 174 atoms and have Δ E int in the range of 60–100 kcal/mol, depending on the functional and basis set.…”

Section: Resultsmentioning

confidence: 99%

“…We examine several layered trimers of polythiophene ( n PT, meaning n thiophene units) with graphene nanoribbons: (5PT)(C 38 H 22 )(5PT), (5PT)(C 59 H 20 )(5PT), and (7PT)(C 46 H 26 )(7PT). Geometries are taken from ref and are provided in the Supporting Information. As representative functionals, we consider M06-2X and ωB97M-V using a subset of the basis sets examined above, mostly representative of practical choices for large systems but including the high-quality def2-TZVPD basis set.…”

Section: Resultsmentioning

confidence: 99%

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Systematic Evaluation of Counterpoise Correction in Density Functional Theory

Gray

Bowling

Herbert

2022

J. Chem. Theory Comput.

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A widespread belief persists that the Boys–Bernardi function counterpoise (CP) procedure “overcorrects” supramolecular interaction energies for the effects of basis-set superposition error. To the extent that this is true for correlated wave function methods, it is usually an artifact of low-quality basis sets. The question has not been considered systematically in the context of density functional theory, however, where basis-set convergence is generally less problematic. We present a systematic assessment of the CP procedure for a representative set of functionals and basis sets, considering both benchmark data sets of small dimers and larger supramolecular complexes. The latter include layered composite polymers with ∼150 atoms and ligand–protein models with ∼300 atoms. Provided that CP correction is used, we find that intermolecular interaction energies of nearly complete-basis quality can be obtained using only double-ζ basis sets. This is less expensive as compared to triple-ζ basis sets without CP correction. CP-corrected interaction energies are less sensitive to the presence of diffuse basis functions as compared to uncorrected energies, which is important because diffuse functions are expensive and often numerically problematic for large systems. Our results upend the conventional wisdom that CP “overcorrects” for basis-set incompleteness. In small basis sets, CP correction is mandatory in order to demonstrate that the results do not rest on error cancellation.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

Gray

Bowling

Herbert

2022

J. Chem. Theory Comput.

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“…The test set has been selected having in mind that graphene clusters and similar species attract a lot of attention also in the context of modeling the interaction of graphene with small molecules, see. e.g., refs ,. The idea of using fullerenes doped with boron and nitrogen has been taken from ref , where the properties of alchemical fullerenes were studied.…”

Section: Computational Detailsmentioning

confidence: 99%

AROFRAG─A Systematic Approach for Fragmentation of Aromatic Molecules

Masoumifeshani,

Korona

2024

J. Chem. Theory Comput.

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We present a new systematic fragmentation scheme of polycyclic aromatic hydrocarbons (PAHs), including fullerenes and nanotubes, based on an idea to treat a sextet ring as a single unbreakable unit so that the basic unit of aromaticity remains preserved upon fragmentation. In the approach, denoted as AROFRAG (from aromatic fragmentation), a set of predefined elementary subsystems, such as naphthalene and biphenyl in the first model and larger PAHs in the second and third models, is generated with appropriate weights with the aim of reproducing the structure of the original molecule. The energies of the molecules are approximated as weighted sums of the energies of these subsystems. For symmetric cases, e.g., fullerenes, the point-group symmetry is preserved during the decomposition. The AROFRAG is used in conjunction with the molecule-in-molecule (MIM) technique to obtain an accurate description of the electronic energies. The new approach has been applied for selected graphene structures and fullerene doped with boron and nitrogen atoms, for which isomerization energies were calculated, as well as for several nanotubes and regular fullerene molecules. The combination of the third AROFRAG model and the MIM approach leads to the reproduction of electronic energies with a few milli-hartree accuracy at a fraction of the computational cost of the original method.

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Section: Large Complexesmentioning

confidence: 99%

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

Gray

Bowling

Herbert

2022

Preprint

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A widespread belief persists that the Boys-Bernardi function counterpoise (CP) procedure "overcorrects" supramolecular interaction energies for the effects of basis-set superposition error. To the extent that this is true for correlated wave function methods, it is usually an artifact of low-quality basis sets, but the question has not been considered systematically in the context of density functional theory (DFT) where basis-set convergence is generally less problematic. We present a systematic assessment of the CP procedure for a representative set of functionals and basis sets, considering both benchmark data sets of small dimers as well as larger supramolecular complexes including layered composite polymers with ~150 atoms and ligand--protein models with ~300 atoms. We find that intermolecular interaction energies approaching complete-basis quality can be obtained using only double-zeta basis sets, provided that CP correction is applied. This is less expensive as compared to using triple-zeta basis sets without CP correction. CP-corrected interaction energies are also less sensitive to the presence of diffuse basis functions as compared to uncorrected energies, which is important given that diffuse functions are expensive and often numerically problematic for large systems. Our results upend the conventional wisdom that CP "overcorrects" for basis-set incompleteness. In small basis sets, CP correction is mandatory in order to demonstrate that the results do not rest on error cancellation.

show abstract

Theoretical Approach to Evaluate the Gas-Sensing Performance of Graphene Nanoribbon/Oligothiophene Composites

Cited by 12 publications

References 83 publications

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

AROFRAG─A Systematic Approach for Fragmentation of Aromatic Molecules

Systematic Evaluation of Counterpoise Correction in Density Functional Theory

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