V.V. Belyaev1, A.S. Solomatin2, V.A. Avdeenkov3, A.V. Kazak4

1State University of Education (Moscow, Russia)

1,3Peoples' Friendship University of Russia (Moscow, Russia)

2Dmitry Mendeleev University of Chemical Technology of Russia (Moscow, Russia)

3Moscow University "Synergy" (Moscow, Russia)

4Ivanovsky State University (Ivanovo, Russia)

4Kurchatov Complex of Crystallography and Photonics, Kurchatov Institute (Moscow, Russia)

1vic_belyaev@mail.ru, vv.belyaev@guppros.ru, 2sotrudnica_unc@mail.ru, 3wladimirawdejenkow@mail.ru, 4alexkazak86@gmail.com

Charge carrier mobility remains the critical parameter that fundamentally limits the performance of organic semiconductor-based devices in modern information and measurement systems. Despite significant progress in the synthesis of new organic materials and the development of device architectures, establishing quantitative relationships between molecular structure, packing arrangements, and transport properties continues to be one of the central challenges in the physics of organic materials. The hopping transport mechanism dominant in disordered organic systems differs fundamentally from band transport in conventional inorganic semiconductors, making theoretical description particularly complex. Existing theoretical frameworks, such as the Gaussian disorder model and its extensions, operate with phenomenological parameters whose physical meaning is directly related to intermolecular interactions and spatial organization of molecules. However, these parameters are typically extracted from experimental data rather than predicted from molecular structure. To bridge this gap and enable rational design of high-mobility organic semiconductors, direct modeling of intermolecular interactions at the atomistic level is essential.

The aim of this work is to investigate charge carrier mobility in organic semiconductors using the extended Gaussian disorder model and to quantitatively determine intermolecular interaction energies for naphthalocyanines and subphthalocyanines using the atom-atom potential method, with subsequent correlation of the obtained energetic parameters with transport characteristics.

Computer simulations revealed that mobility demonstrates an activation temperature dependence characteristic of the hopping mechanism, exhibits a quadratic dependence on the lattice constant (μ₀ µ a02), and decreases exponentially with increasing disorder parameter σ. An increase in σ from 0.1 to 0.15 eV results in a mobility change of several orders of magnitude at room temperature, highlighting the critical importance of molecular ordering. The atom-atom potential method was employed to calculate intermolecular interaction energies for six compounds based on naphthalocyanines and subphthalocyanines as a function of mutual molecular orientation. For all investigated compounds, a pronounced global energy minimum was identified, corresponding to columnar packing with nearly parallel orientation of macrocyclic planes (θ ≈ 0−10°) and small lateral displacement (φ ≈ 0−10°), which agrees well with known crystallographic data. The energy variation range upon changing molecular orientation is 104−105 J/mol (0.1−1.2 eV), which quantitatively correlates with the characteristic values of the disorder parameter σ = 0.1−0.15 eV used in the extended Gaussian disorder model and is also consistent with parameters obtained within the delocalized polaron diffusion model. The optimal intermolecular distance for all compounds is dopt ≈ 3.3…3.7 Å, which corresponds to the characteristic π−π interaction distance for effective orbital overlap in columnar assemblies. Variation of dopt within this range changes mobility by approximately 20% according to the quadratic dependence, demonstrating the sensitivity of transport properties to packing geometry.

The quantitative agreement between atomistically calculated intermolecular interaction energies and phenomenological disorder parameters validates the atom-atom potential method as an efficient tool for preliminary screening of promising molecular structures for organic semiconductors. The results confirm the critical role of molecular packing and mutual orientation in ensuring efficient charge transport and can be used in the development of next-generation organic materials for electronic information and measurement devices. The computational approach presented here offers a practical pathway from molecular design to prediction of macroscopic transport properties without resource-intensive quantum chemical calculations.

Belyaev V.V., Solomatin A.S., Avdeenkov V.A., Kazak A.V. Modeling of organic semiconductors for electronic devices // Information-measuring and Control Systems. 2026. V. 24. № 4. P. 67−76. DOI: https://doi.org/10.18127/j20700814-202604-08

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