Applicability of perturbed matrix method for charge transfer studies at bio/metallic interfaces: a case of azurin

0571449 - ÚOCHB 2024 RIV GB eng J - Journal Article
Kontkanen, O. V. - Biriukov, Denys - Futera, Z.
Applicability of perturbed matrix method for charge transfer studies at bio/metallic interfaces: a case of azurin.
Physical Chemistry Chemical Physics. Roč. 25, č. 17 (2023), s. 12479-12489. ISSN 1463-9076. E-ISSN 1463-9084
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61388963
Keywords : biological electron transfer * density functional theory * reorganization free energies
OECD category: Physical chemistry
Impact factor: 3.3, year: 2022
Method of publishing: Limited access
https://doi.org/10.1039/D3CP00197K

As the field of nanoelectronics based on biomolecules such as peptides and proteins rapidly grows, there is a need for robust computational methods able to reliably predict charge transfer properties at bio/metallic interfaces. Traditionally, hybrid quantum-mechanical/molecular-mechanical techniques are employed for systems where the electron hopping transfer mechanism is applicable to determine physical parameters controlling the thermodynamics and kinetics of charge transfer processes. However, these approaches are limited by a relatively high computational cost when extensive sampling of a configurational space is required, like in the case of soft biomatter. For these applications, semi-empirical approaches such as the perturbed matrix method (PMM) have been developed and successfully used to study charge-transfer processes in biomolecules. Here, we explore the performance of PMM on prototypical redox-active protein azurin in various environments, from solution to vacuum interfaces with gold surfaces and protein junction. We systematically benchmarked the robustness and convergence of the method with respect to the quantum-centre size, size of the Hamiltonian, number of samples, and level of theory. We show that PMM can adequately capture all the trends associated with the structural and electronic changes related to azurin oxidation at bio/metallic interfaces.
Permanent Link: https://hdl.handle.net/11104/0342666