On the use of a volume constraint to account for thermal expansion effects on the low-frequency vibrations of molecular crystals

Rogers, Fergus J. M.; Radhanpura, Krunal; Horvat, J.; Farrant, David I.

doi:10.1039/d1cp05718a

Cited by 7 publications

(5 citation statements)

References 92 publications

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“…London dispersion interactions were taken into account by using the semi-empirical D3 scheme [ 73 ]. PBE-D3 and B3LYP gave a reasonable description of the LF Raman spectrum of organic crystals in periodic DFT calculations [ 31 , 51 , 53 , 74 , 75 ], while PBEsol was used to study the energetics of molecular crystals [ 76 ]. The space groups and the unit cell parameters of the crystals obtained from the X-Ray diffraction experiment were fixed and the structural relaxations were limited to the positional parameters of the atoms [ 53 ].…”

Section: Methodsmentioning

confidence: 99%

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening

Vener

Kharlanov

Sosorev

2022

IJMS

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Charge transport in crystalline organic semiconductors (OSCs) is considerably hindered by low-frequency vibrations introducing dynamic disorder in the charge transfer integrals. Recently, we have shown that the contributions of various vibrational modes to the dynamic disorder correlate with their Raman intensities and suggested a Raman-based approach for estimation of the dynamic disorder and search for potentially high-mobility OSCs. In the present paper, we showcase this approach by revealing the highest-mobility OSC(s) in two series of crystalline naphthalene diimide derivatives bearing alkyl or cycloalkyl substituents. In contrast to our previous studies, Raman spectra are not measured, but are instead calculated using periodic DFT. As a result, an OSC with a potentially high charge mobility is revealed in each of the two series, and further mobility calculations corroborate this choice. Namely, for the naphthalene diimide derivatives with butyl and cyclopentyl substituents, the estimated room-temperature isotropic electron mobilities are as high as 6 and 15 cm2 V–1 s–1, respectively, in the latter case even exceeding 20 cm2 V–1 s–1 in a two-dimensional plane. Thus, our results highlight the potential of using the calculated Raman spectra to search for high-mobility crystalline OSCs and reveal two promising OSCs, which were previously overlooked.

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Section: Methodsmentioning

confidence: 99%

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening

Vener

Kharlanov

Sosorev

2022

IJMS

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“…It should be emphasized that the analysis of normal vibrations of the cluster structure, obtained as a result of partial optimization usually leads to imaginary frequencies. Therefore, this approximation is hardly applicable for calculating the experimentally observed characteristics of molecular crystals, namely: sublimation enthalpies [17,18,43], IR [80,81] and Raman spectra [68,71].…”

Section: Fast Quantum Approach For Evaluating the Energy Of Intermole...mentioning

confidence: 99%

“…B3LYP and PBE-D3 are the most popular functionals in periodic (solid-state) DFT calculations of organic crystals [12,17,18,81]. These functionals provide a grounded tradeoff between the accuracy and the rate of calculations of experimentally observed properties of multicomponent organic crystals [28,43,68,71].…”

Section: Periodic (Solid-state) Dft Computationsmentioning

confidence: 99%

Fast Quantum Approach for Evaluating the Energy of Non-Covalent Interactions in Molecular Crystals: The Case Study of Intermolecular H-Bonds in Crystalline Peroxosolvates

et al. 2022

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Energy/enthalpy of intermolecular hydrogen bonds (H-bonds) in crystals have been calculated in many papers. Most of the theoretical works used non-periodic models. Their applicability for describing intermolecular H-bonds in solids is not obvious since the crystal environment can strongly change H-bond geometry and energy in comparison with non-periodic models. Periodic DFT computations provide a reasonable description of a number of relevant properties of molecular crystals. However, these methods are quite cumbersome and time-consuming compared to non-periodic calculations. Here, we present a fast quantum approach for estimating the energy/enthalpy of intermolecular H-bonds in crystals. It has been tested on a family of crystalline peroxosolvates in which the H∙∙∙O bond set fills evenly (i.e., without significant gaps) the range of H∙∙∙O distances from ~1.5 to ~2.1 Å typical for strong, moderate, and weak H-bonds. Four of these two-component crystals (peroxosolvates of macrocyclic ethers and creatine) were obtained and structurally characterized for the first time. A critical comparison of the approaches for estimating the energy of intermolecular H-bonds in organic crystals is carried out, and various sources of errors are clarified.

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“…The 6-31G** basis set was used. The space groups and the unit cell parameters of the crystal obtained from the X-ray diffraction experiment were fixed, and the structural relaxations were limited to the positional parameters of the atoms [ 70 , 71 ]. Tolerance on energy controlling the self-consistent field convergence for geometry optimizations and frequency computations was set to 10 −10 and 10 −11 Hartree, respectively.…”

Section: Methodsmentioning

confidence: 99%

Supramolecular Organization in Salts of Riluzole with Dihydroxybenzoic Acids—The Key Role of the Mutual Arrangement of OH Groups

et al. 2023

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Intermolecular interactions, in particular hydrogen bonds, play a key role in crystal engineering. The ability to form hydrogen bonds of various types and strengths causes competition between supramolecular synthons in pharmaceutical multicomponent crystals. In this work, we investigate the influence of positional isomerism on the packing arrangements and the network of hydrogen bonds in multicomponent crystals of the drug riluzole with hydroxyl derivatives of salicylic acid. The supramolecular organization of the riluzole salt containing 2,6-dihydroxybenzoic acid differs from that of the solid forms with 2,4- and 2,5-dihydroxybenzoic acids. Because the second OH group is not at position 6 in the latter crystals, intermolecular charge-assisted hydrogen bonds are formed. According to periodic DFT calculations, the enthalpy of these H-bonds exceeds 30 kJ·mol−1. The positional isomerism appears to have little effect on the enthalpy of the primary supramolecular synthon (65–70 kJ·mol−1), but it does result in the formation of a two-dimensional network of hydrogen bonds and an increase in the overall lattice energy. According to the results of the present study, 2,6-dihydroxybenzoic acid can be treated as a promising counterion for the design of pharmaceutical multicomponent crystals.

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On the use of a volume constraint to account for thermal expansion effects on the low-frequency vibrations of molecular crystals

Abstract: Periodic density-functional theory is used to investigate the effect of cell contraction on the accuracy of simulated terahertz absorption spectra.

Cited by 7 publications

References 92 publications

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening

Fast Quantum Approach for Evaluating the Energy of Non-Covalent Interactions in Molecular Crystals: The Case Study of Intermolecular H-Bonds in Crystalline Peroxosolvates

Supramolecular Organization in Salts of Riluzole with Dihydroxybenzoic Acids—The Key Role of the Mutual Arrangement of OH Groups

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