Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps
Само за регистроване кориснике
2021
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
The requirement for controllable frontier orbital energy shift in single-molecule devices based on electronic (tunneling) transport yielded several rules for device design that lean on molecular level pinning to the electrochemical potential of nano-electrodes. We previously found that the pinning (designated as the strong pinning) was the consequence of the bias-induced molecular charge accumulation related to the hybridization of the highest occupied molecular orbital (HOMO) with one of the electrodes. However, in the wide bias range, only "partial" pinning (designated as the weak pinning) happens. In this work, we address the bias-induced shift of molecular orbitals in a weak pinning regime, where no hybridization or covalent bonds with electrodes exist. We found using density functional theory coupled with non-equilibrium Green's functions that the energy shift of frontier molecular orbitals of benzene and nicotine, placed between H-terminated (3, 3) CNTs, in weak pinning regime, i...s driven only by the electrostatic potential energy of an empty gap. For nicotine, whose HOMO and LUMO (lowest unoccupied molecular orbital) are located on different sides of the gap center, we show that the HOMO-LUMO energy gap changes with bias. We developed a theoretical model of a dielectric in a gap to depict this behavior. Application-wise, we expect that the weak pinning effect would be observable in novel single-molecule sensors based on electronic transport and molecular rectifying as long as the system exhibits a non-resonant behavior, and could serve for molecular gap tuning in single-molecule readout such as DNA, RNA and protein sequencing, or harmful single-molecule detection in gas phase.
Кључне речи:
Single-molecule / Molecular level pinning / Modeling and simulation / Electrostatic potential / Electronic transport / DFT plus NEGF / Carbon nanotubesИзвор:
Journal of Nanoparticle Research, 2021, 23, 1Издавач:
- Springer, Dordrecht
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200053 (Универзитет у Београду, Институт за мултидисциплинарна истраживања) (RS-MESTD-inst-2020-200053)
- Swiss National Science Foundation (SCOPES project)Swiss National Science Foundation (SNSF) [152406]
- FP7-NMP, project acronym nanoDNAsequencing [GA214840]
DOI: 10.1007/s11051-021-05139-y
ISSN: 1388-0764
WoS: 000616413500010
Scopus: 2-s2.0-85100211702
Институција/група
Institut za multidisciplinarna istraživanjaTY - JOUR AU - Djurišić, Ivana AU - Dražić, Miloš AU - Tomović, Aleksandar AU - Jovanović, Vladimir P. AU - Žikić, Radomir PY - 2021 UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/1412 AB - The requirement for controllable frontier orbital energy shift in single-molecule devices based on electronic (tunneling) transport yielded several rules for device design that lean on molecular level pinning to the electrochemical potential of nano-electrodes. We previously found that the pinning (designated as the strong pinning) was the consequence of the bias-induced molecular charge accumulation related to the hybridization of the highest occupied molecular orbital (HOMO) with one of the electrodes. However, in the wide bias range, only "partial" pinning (designated as the weak pinning) happens. In this work, we address the bias-induced shift of molecular orbitals in a weak pinning regime, where no hybridization or covalent bonds with electrodes exist. We found using density functional theory coupled with non-equilibrium Green's functions that the energy shift of frontier molecular orbitals of benzene and nicotine, placed between H-terminated (3, 3) CNTs, in weak pinning regime, is driven only by the electrostatic potential energy of an empty gap. For nicotine, whose HOMO and LUMO (lowest unoccupied molecular orbital) are located on different sides of the gap center, we show that the HOMO-LUMO energy gap changes with bias. We developed a theoretical model of a dielectric in a gap to depict this behavior. Application-wise, we expect that the weak pinning effect would be observable in novel single-molecule sensors based on electronic transport and molecular rectifying as long as the system exhibits a non-resonant behavior, and could serve for molecular gap tuning in single-molecule readout such as DNA, RNA and protein sequencing, or harmful single-molecule detection in gas phase. PB - Springer, Dordrecht T2 - Journal of Nanoparticle Research T1 - Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps IS - 1 VL - 23 DO - 10.1007/s11051-021-05139-y ER -
@article{ author = "Djurišić, Ivana and Dražić, Miloš and Tomović, Aleksandar and Jovanović, Vladimir P. and Žikić, Radomir", year = "2021", abstract = "The requirement for controllable frontier orbital energy shift in single-molecule devices based on electronic (tunneling) transport yielded several rules for device design that lean on molecular level pinning to the electrochemical potential of nano-electrodes. We previously found that the pinning (designated as the strong pinning) was the consequence of the bias-induced molecular charge accumulation related to the hybridization of the highest occupied molecular orbital (HOMO) with one of the electrodes. However, in the wide bias range, only "partial" pinning (designated as the weak pinning) happens. In this work, we address the bias-induced shift of molecular orbitals in a weak pinning regime, where no hybridization or covalent bonds with electrodes exist. We found using density functional theory coupled with non-equilibrium Green's functions that the energy shift of frontier molecular orbitals of benzene and nicotine, placed between H-terminated (3, 3) CNTs, in weak pinning regime, is driven only by the electrostatic potential energy of an empty gap. For nicotine, whose HOMO and LUMO (lowest unoccupied molecular orbital) are located on different sides of the gap center, we show that the HOMO-LUMO energy gap changes with bias. We developed a theoretical model of a dielectric in a gap to depict this behavior. Application-wise, we expect that the weak pinning effect would be observable in novel single-molecule sensors based on electronic transport and molecular rectifying as long as the system exhibits a non-resonant behavior, and could serve for molecular gap tuning in single-molecule readout such as DNA, RNA and protein sequencing, or harmful single-molecule detection in gas phase.", publisher = "Springer, Dordrecht", journal = "Journal of Nanoparticle Research", title = "Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps", number = "1", volume = "23", doi = "10.1007/s11051-021-05139-y" }
Djurišić, I., Dražić, M., Tomović, A., Jovanović, V. P.,& Žikić, R.. (2021). Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps. in Journal of Nanoparticle Research Springer, Dordrecht., 23(1). https://doi.org/10.1007/s11051-021-05139-y
Djurišić I, Dražić M, Tomović A, Jovanović VP, Žikić R. Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps. in Journal of Nanoparticle Research. 2021;23(1). doi:10.1007/s11051-021-05139-y .
Djurišić, Ivana, Dražić, Miloš, Tomović, Aleksandar, Jovanović, Vladimir P., Žikić, Radomir, "Electrostatically driven energy shift of molecular orbitals of benzene and nicotine in carbon nanotube gaps" in Journal of Nanoparticle Research, 23, no. 1 (2021), https://doi.org/10.1007/s11051-021-05139-y . .