Accurate Modelling of Group Electrostatic Potential and Distributed Polarizability in Dipeptides

Jabłuszewska, Angelika; Krawczuk, Anna; Santos, Leonardo H. R. Dos; Macchi, Piero

doi:10.1002/cphc.202000441

Cited by 10 publications

(19 citation statements)

References 66 publications

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“…However, in the following we will discuss the numerical results of the two invariants of the polarizability tensor, namely, the average isotropic and anisotropic polarizabilities, defined as and respectively. Atomic polarizability ellipsoids , could also be represented from the OIEB decomposition. Notice that upon decomposition of the polarizability tensor, the atomic isotropic polarizabilities (α hereafter unless otherwise stated) should add up to the total average isotropic polarizability.…”

Section: Illustrative Resultsmentioning

confidence: 99%

Origin-Independent Decomposition of the Static Polarizability

Montilla

Luis

Salvador

2021

J. Chem. Theory Comput.

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Real-space analysis tools afford additive and transferable contributions of atoms to molecular properties. In the case of the molecular (hyper)polarizabilities, the atomic contributions that have been derived so far include a charge-transfer term that is origin-dependent. In this letter, we present the first genuinely origin-independent energy-based (OIEB) methodology for the decomposition of the static (hyper)polarizabilities that benefits from real-space molecular energy decomposition schemes, focusing on the static polarizability and showing that extension to static hyperpolarizabilities is straightforward. The numerical realization of the OIEB method shows the expected origin independence, atomic additivity, and transferability of atomic and functional group polarizability tensors. Furthermore, the OIEB atomic (fragment) polarizability tensors are symmetric by definition.

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Section: Illustrative Resultsmentioning

confidence: 99%

Origin-Independent Decomposition of the Static Polarizability

Montilla

Luis

Salvador

2021

J. Chem. Theory Comput.

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“…In the former case, this is caused by the inability of ADIM to account for relatively strong hence directional hydrogen bonds, whereas in the latter case the point dipole method fails on reproducing the polarization of a very large species. The polarizability of ester groups in methylbenzoate is better reproduced because it is not much affected by the near intermolecular environment as this functional group is not located in the extremities of the molecule, thus polarization and charge-transfer effects due to intermolecular neighbors play a less significant role . It is noteworthy that the polarizability of carboxylic groups in succinic acid is almost entirely reproduced by ADIM in view of the fact that the −COOH···O(HO)C– hydrogen bonds are so strong and short as to behave almost like intramolecular contacts, therefore, shielding polarization effects from the rest of the molecules nearby.…”

Section: Resultsmentioning

confidence: 99%

Crystal Field Effects on Atomic and Functional-Group Distributed Polarizabilities of Molecular Materials

2020

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To rationally design new molecular materials with desirable linear optical properties, such as refractive index or birefringence, we investigated how atomic and functional-group polarizability tensors of prototypical molecules respond to crystal field effects. By building finite aggregates of urea, succinic acid, p-nitroaniline, 4-mercaptopyridine, or methylbenzoate, and by partitioning the cluster electronic density using quantum theory of atoms in molecules, we could extract atoms and functional groups from the aggregates and estimate their polarizability enhancements with respect to values calculated for molecules in isolation. The isotropic polarizability and its anisotropy for the molecular building blocks are used to understand the functional-group sources of optical properties in these model systems, which could help the synthetic chemist to fabricate efficient materials. This analysis is complemented by benchmarking density functionals for atomic distributed polarizabilities in gas phase, by comparing the results with refractive-index calculations under periodic boundary conditions, and by estimating functional-group optical properties from a classical electrostatic atom–dipole interaction model.

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“…Given the additivity of QTAIM, the summation of V(r; Ω) over all basins provides the molecular electrostatic potential mapping. 32 Since the electric properties estimated from ADIM show good correspondence with those calculated from quantum mechanics on the aggregates, it reveals itself as an interesting method to estimate changes in electrostatic potentials caused by disturbances on neighboring atoms. Molecular clusters can be seen in Figure 1, along with their distributed polarizabilities.…”

Section: ■ Theoretical Methodsmentioning

confidence: 88%

“…From the distributed atomic moments, we also calculated electrostatic potentials for the atomic basins as in which r is a position vector at any point in space. Given the additivity of QTAIM, the summation of V ( r ; Ω) over all basins provides the molecular electrostatic potential mapping . Since the electric properties estimated from ADIM show good correspondence with those calculated from quantum mechanics on the aggregates, it reveals itself as an interesting method to estimate changes in electrostatic potentials caused by disturbances on neighboring atoms.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Accurate Atom–Dipole Interaction Model for Prediction of Electro-optical Properties: From van der Waals Aggregates to Covalently Bonded Clusters

2021

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This work aims at the accurate estimation of the electrooptical properties of atoms and functional groups in organic crystals. A better understanding of the nature of building blocks and the way they interact with each other enables more efficient prediction of self-assembly, and thus physical properties in condensed matter. We propose a modified version of an atom−dipole interaction model that is based on atomic dipole moments calculated from the quantum theory of atoms in molecules. The method is very reliable for the prediction of various optical and electric properties in diverse chemical environments, ranging from hydrocarbon molecules bonded by dispersive interactions to polar rings connected by hydrogen bonds, or even polymeric structures whose monomers are covalently linked. Distributed polarizabilities and electrostatic potentials are compared to those obtained using a complete quantum-mechanical approach on finite-size aggregates. Our electrostatic approximation recovers isotropic polarizabilities with an accuracy of ca. 5 au and electrostatic potentials of ca. 0.05 au, even in the worst-case scenario in which polarization and chargetransfer effects are large. Functional groups are highly exportable, estimating the properties of small peptides and polyaromatics with a maximum deviation as low as ca. 15%.

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Accurate Modelling of Group Electrostatic Potential and Distributed Polarizability in Dipeptides

Cited by 10 publications

References 66 publications

Origin-Independent Decomposition of the Static Polarizability

Origin-Independent Decomposition of the Static Polarizability

Crystal Field Effects on Atomic and Functional-Group Distributed Polarizabilities of Molecular Materials

Accurate Atom–Dipole Interaction Model for Prediction of Electro-optical Properties: From van der Waals Aggregates to Covalently Bonded Clusters

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