Article
Chemistry, Multidisciplinary
Ping Duan, Yaping Wang, Lichuan Chen, Kai Qu, Junyang Liu, Qian-Chong Zhang, Zhong-Ning Chen, Wenjing Hong
Summary: Investigating the correlations of electron transport between multiple channels shows promise for the design of molecule-scale circuits with logic operations. The modulation of electronegativity provides an effective method for controlling electron transport through multiple channels and exploring their interactions. Experimental and theoretical studies suggest that electronegativity has a more significant effect on electron transport in dual-channel structures.
Article
Nanoscience & Nanotechnology
Shintaro Fujii, Enrique Montes, Haruna Cho, Yi Yue, Masaaki Koike, Tomoaki Nishino, Hector Vazquez, Manabu Kiguchi
Summary: In this paper, the tuning of the thermopower of single-molecule junctions of fullerene, 4,4'-bipyridine, and p-phenylenediamine using scanning tunneling microscopy-based break junction technique is demonstrated. The thermoelectric voltage of the junction is tuned by mechanically controlling the tip-electrode separation distance. The atomistic simulations illustrate the shifts in the conduction orbital energies induced by the mechanical compression of the junctions.
ADVANCED ELECTRONIC MATERIALS
(2022)
Article
Electrochemistry
Anas Akhtar, Umar Rashid, Charu Seth, Sunil Kumar, Peter Broekmann, Veerabhadrarao Kaliginedi
Summary: This review introduces the concept of electrochemical gating and its applicability in fabricating functional molecular devices, emphasizing the importance of ionic liquids in the electrochemical environment and discussing the experimental testbeds for investigating electrochemically gated molecular junctions. It also stresses the manifestation of quantum interference effects and the relevance of electrochemically gated charge transport in biological systems, while outlining future research directions in the field.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Ya-Hao Wang, Feng Yan, Dong-Fang Li, Yan-Feng Xi, Rui Cao, Ju-Fang Zheng, Yong Shao, Shan Jin, Jing-Zhe Chen, Xiao-Shun Zhou
Summary: This study presents a new strategy to improve the electrochemical gating efficiency of single-molecule conductance, achieving a significant gating ratio through fused molecular structures. The research demonstrates that electrochemical gating performance can be significantly modulated by adjusting the alignment of the conducting orbital of the heterocyclic molecule relative to the metal Fermi energy.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Shuhui Tao, Qian Zhang, Andrea Vezzoli, Cezhou Zhao, Chun Zhao, Simon J. Higgins, Alexander Smogunov, Yannick J. Dappe, Richard J. Nichols, Li Yang
Summary: In this study, the single-molecular conductance of a redox active viologen molecular bridge between Au|graphene electrodes was investigated in an electrochemical gating configuration. The results showed a clear off-on-off conductance switching behavior through gating of the redox state. The study also revealed that substituting one gold contact for a graphene one had a significant impact on the junction conductance values. The experimental data was compared against two theoretical models, providing insights into the charge state evolution of the molecule with electrode potential and the sequential charge transport through the redox center in the adiabatic limit. This work opens perspectives for graphene-based molecular transistors with more effective gating and a better understanding of electrochemical electron transfer at the single molecular level.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Hector Vazquez
Summary: This method uses density functional theory to calculate the tunneling conductance of single molecule junctions, simplifying the model and reducing computational costs significantly, while also quantifying the relationship between molecular structure and conductance.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Multidisciplinary Sciences
Zhuang Yan, Xingxing Li, Yusen Li, Chuangcheng Jia, Na Xin, Peihui Li, Linan Meng, Miao Zhang, Long Chen, Jinlong Yang, Rongming Wang, Xuefeng Guo
Summary: In this study, we demonstrate two configurations of a graphene-porphyrin-graphene single-molecule junction (SMJ) driven by electric field and proton transfer. The transistor configuration shows exceptional field-effect performance with high on/off ratio and gate efficiency. The other configuration reveals controllable proton transfer and tautomerization switching. This work provides insights into constructing multifunctional molecular nanocircuits and understanding the intrinsic properties of matters at the molecular scale.
Article
Chemistry, Multidisciplinary
Zhichao Pan, Lichuan Chen, Chun Tang, Yong Hu, Saisai Yuan, Tengyang Gao, Jie Shi, Jia Shi, Yang Yang, Wenjing Hong
Summary: The study shows that flicker noise can indicate the evolution of charge transport mechanisms in single-molecule break junction process, with flicker noise components of the molecule junction showing time evolution behavior during dynamic break junction process. Furthermore, the investigation reveals a transition in charge transport mechanism from through-space to through-bond transport during dynamic break junction process, with through-space transport dominating again when the junction is about to rupture.
Article
Chemistry, Physical
Luchun Lin, Chun Tang, Gang Dong, Zhixin Chen, Zhichao Pan, Junyang Liu, Yang Yang, Jia Shi, Rongrong Ji, Wenjing Hong
Summary: The single-molecule break junction technique allows for exploring charge transport phenomena at the ultimate scale of a single molecule, but traditional data analysis methods may overlook important conductance variations. A customized spectral clustering method combined with the evaluation of the Calinski-Harabasz index has been demonstrated to be suitable for analyzing large datasets and automatically extracting different molecular junction conformations, offering a promising algorithm for junction conformation analysis in massive break junction data.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Multidisciplinary
Joel G. Fallaque, Sandra Rodriguez-Gonzalez, Cristina Diaz, Fernando Martin
Summary: This study presents a systematic theoretical investigation of the conductance of different disubstituted acenes, revealing that the relative variation of conductance can be well explained by the variations of HOMO energies as predicted by a simple extended-Huckel approach. The model accurately predicts the conductance trends among different types of acenes and linkers, providing insights into engineering molecular conductance. This approach is expected to be useful in predicting trends in the conductance of a wide range of disubstituted acene isomers.
Article
Biochemistry & Molecular Biology
Ziye Wu, Peng Cui, Mingsen Deng
Summary: This paper presents an effective strategy to enhance the multifunctionality and switching performance of diarylethene-based molecular devices. Through molecular engineering design and theoretical calculations, the transport behaviors of molecules with different substituents are investigated, and a rectification function that can be switched on/off through photoisomerization is proposed.
Article
Chemistry, Physical
Riku Tuovinen, Robert van Leeuwen, Enrico Perfetto, Gianluca Stefanucci
Summary: The generalized Kadanoff-Baym ansatz (GKBA) provides a cost-effective way to simulate out-of-equilibrium quantum systems. Recent advancements have overcome the limitation of neglecting initial correlations in the conventional GKBA approach. In the context of quantum transport, a further extension of the GKBA approach is needed to account for the contacted nature of the initial state.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Ling-Yan Ai, Jing-Jing Guo, Jing Wang, Hui-Yan Zhao, Ying Liu
Summary: Based on density-functional theory calculations, a polyhedron molecule, Re12C80 cage, was proposed and showed topological analogy to Catalan pentagonal hexecontahedron. The geometric topology of Re12C80 molecule retains integrity when the effective temperature is up to 782 K. Its electronic structure shows the presence of sp2-like hybrid orbital for carbon atom and d orbital characteristics for rhenium atom. The large hollow space of Re12C80 cage can be utilized to encapsulate other atoms or small molecules. The proposal of Re12C80 molecular structure can contribute to the enrichment and expansion of highly symmetric polyhedral molecules.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Enrique Montes, Hector Vazquez
Summary: Using density functional theory (DFT), the electronic and conducting properties of benzenediamine connected to gold electrodes via different tip structures were investigated. Different binding motifs and junction spectral properties were examined, with corrections to molecular resonances at the junction based on atomistic structure of the tip. DFT-based transmission spectra approximated by a Lorentzian model involving only the highest occupied molecular orbital (HOMO) can achieve conductance values in quantitative agreement with previous experiments.
APPLIED SCIENCES-BASEL
(2021)
Article
Chemistry, Multidisciplinary
Jie Bai, Xiaohui Li, Zhiyu Zhu, Yan Zheng, Wenjing Hong
Summary: Single-molecule electrochemical transistors are novel molecular devices in which the tunneling current through the single-molecule junction is modulated by the electrochemical gate, enriching the functions of the transistor devices. This review focuses on the transfer characteristics, performance, and prospects for the fabrication of integrated devices of several typical types of single-molecule electrochemical transistors.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Woojung Lee, Shayan Louie, Austin M. Evans, Nicholas M. Orchanian, Ilana B. Stone, Boyuan Zhang, Yujing Wei, Xavier Roy, Colin Nuckolls, Latha Venkataraman
Summary: This study demonstrates that dynamic molecular structures lead to temperature-dependent conductance in molecular wires. Thermally activated dihedral rotations increase the probability of molecular wires being in a planar conformation, enhancing tunneling probability. Longer molecular wires with more rotational pivot points exhibit larger temperature dependence on conductance.
Article
Chemistry, Multidisciplinary
Liang Li, Jonathan Z. Low, Jan Wilhelm, Guanming Liao, Suman Gunasekaran, Claudia R. Prindle, Rachel L. Starr, Dorothea Golze, Colin Nuckolls, Michael L. Steigerwald, Ferdinand Evers, Luis M. Campos, Xiaodong Yin, Latha Venkataraman
Summary: A family of oligophenylene-bridged bis(triarylamines) with tunable and stable mono- or di-radicaloid character was studied, showing reversed conductance decay with increasing length for oxidized wires, indicating non-classical quasi-metallic behavior.
Article
Chemistry, Physical
Liang Li, Suman Gunasekaran, Yujing Wei, Colin Nuckolls, Latha Venkataraman
Summary: This study investigates the conductance properties of 1D TIs such as polyacetylene using a tight-binding approach and discovers the phenomenon of reversed conductance decay in the short chain limit. The impact of edge states on the transmission of single-molecule junctions is analyzed to explain this conductance trend, and methods for tuning the self-energy and on-site energy of edge sites to create longer wires with reversed conductance decays are proposed.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Surya T. Parker, Alex Smith, Alexander C. Forse, Wei-Chih Liao, Florian Brown-Altvater, Rebecca L. Siegelman, Eugene J. Kim, Nicholas A. Zill, Wenjun Zhang, Jeffrey B. Neaton, Jeffrey A. Reimer, Jeffrey R. Long
Summary: In this study, the stability and CO2 capture performance of diamine-appended Mg2(dobpdc) metal-organic frameworks in the presence of SO2 were investigated. It was found that the materials with primary,primary diamines exhibited better stability to humid SO2. The reaction between SO2 and the primary,secondary or primary,tertiary diamines resulted in material degradation, while the reaction with primary,primary diamines did not affect the metal-diamine bond.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Panagiota Perlepe, Itziar Oyarzabal, Laura Voigt, Mariusz Kubus, Daniel N. Woodruff, Sebastian E. Reyes-Lillo, Michael L. Aubrey, Philippe Negrier, Mathieu Rouzieres, Fabrice Wilhelm, Andrei Rogalev, Jeffrey B. Neaton, Jeffrey R. Long, Corine Mathoniere, Baptiste Vignolle, Kasper S. Pedersen, Rodolphe Clerac
Summary: The electronic synergy between metal ions and organic linkers is essential for engineering molecule-based materials with high electrical conductivity and metallicity. This study demonstrates the crucial role of metal ions in tuning the electronic properties of such materials, leading to high room-temperature conductivity and the existence of a correlated metal state.
NATURE COMMUNICATIONS
(2022)
Article
Physics, Multidisciplinary
Vivekanand Shukla, Yang Jiao, Jung-Hoon Lee, Elsebeth Schroeder, Jeffrey B. Neaton, Per Hyldgaard
Summary: We introduce a new general-purpose van der Waals density functional, vdW-DF2-ahbr, which combines vdW-DF2 correlation with a screened Fock exchange. It successfully resolves spurious exchange binding and density-driven errors, significantly improving the performance of existing vdW-DFs for molecular problems.
Article
Chemistry, Physical
Lorenzo Gigli, Max Veit, Michele Kotiuga, Giovanni Pizzi, Nicola Marzari, Michele Ceriotti
Summary: The study develops an integrated machine learning model that accurately describes the structural, energetic, and functional properties of ferroelectric materials, and allows for the investigation of the microscopic mechanism of ferroelectric transition without the need for a coarse-grained description. The main driver of the ferroelectric transition in barium titanate is found to be the order-disorder transition of the off-centered states.
NPJ COMPUTATIONAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Liang Li, Shayan Louie, Austin M. Evans, Elena Meirzadeh, Colin Nuckolls, Latha Venkataraman
Summary: Molecular one-dimensional topological insulators (1D TIs) that conduct through low-lying topological edge states have potential for nanoelectronic devices. To observe these effects at longer lengths, we design topological oligo[n]emeraldine wires using short 1D TIs as building blocks. As the wire length increases, the number of topological states increases, enabling increased electronic transmission. The longest oligo[7]emeraldine with doped topological states has over 106 enhancements in transmission compared to its pristine form.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yujing Wei, Liang Li, Julia E. Greenwald, Latha Venkataraman
Summary: Understanding the relationship between molecular geometry and electronic properties of single-molecule junctions is challenging. In this study, we investigated this relationship by applying a sinusoidal modulation to the molecular junction electrode position. We found that junctions formed with molecules having different molecule-electrode interfaces exhibited statistically distinguishable Fourier-transformed conductances. Our findings suggest that voltage-modulated van der Waals interactions play a significant role in the conductance of single-molecule junctions.
Article
Nanoscience & Nanotechnology
Aditya Sood, Jonah B. Haber, Johan Carlstrom, Elizabeth A. Peterson, Elyse Barre, Johnathan D. Georgaras, Alexander H. M. Reid, Xiaozhe Shen, Marc E. Zajac, Emma C. Regan, Jie Yang, Takashi Taniguchi, Kenji Watanabe, Feng Wang, Xijie Wang, Jeffrey B. Neaton, Tony F. Heinz, Aaron M. Lindenberg, Felipe H. da Jornada, Archana Raja
Summary: In this study, lattice dynamics in photoexcited WSe2/WS2 heterostructures were directly visualized using femtosecond electron diffraction. It was found that both WSe2 and WS2 were heated simultaneously on a picosecond timescale, which cannot be explained by phonon transport across the interface. First-principles calculations revealed a fast channel involving layer-hybridized electronic states, enabling phonon-assisted interlayer transfer of photoexcited electrons. Phonons were emitted in both layers on the femtosecond timescale via this channel, consistent with the simultaneous lattice heating observed experimentally. Strong electron-phonon coupling via layer-hybridized electronic states was identified as a novel route for controlling energy transport across atomic junctions.
NATURE NANOTECHNOLOGY
(2023)
Article
Chemistry, Physical
Iurii Timrov, Michele Kotiuga, Nicola Marzari
Summary: Using density-functional theory with extended Hubbard functionals-DFT+U+V, we investigated the properties of spinel-type cathode materials LixMn2O4 and LixMn1.5Ni0.5O4. Our results showed that the U parameter is crucial for obtaining the right trends in material properties, while the V parameter is essential for a quantitative description of the structural and electronic properties, as well as Li-intercalation voltages. This work enables reliable first-principles studies of other families of cathode materials without relying on empirical fitting or calibration procedures.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Correction
Multidisciplinary Sciences
X. Yin, Y. Zang, L. Zhu, J. Z. Low, Z. F. Liu, J. Cui, J. B. Neaton, L. Venkataraman, L. M. Campos
Article
Chemistry, Multidisciplinary
Lan Zhou, Elizabeth A. Peterson, Karun K. Rao, Yubing Lu, Xiang Li, Yungchieh Lai, Sage R. Bauers, Matthias H. Richter, Kevin Kan, Yu Wang, Paul F. Newhouse, Junko Yano, Jeffrey B. Neaton, Michal Bajdich, John M. Gregoire
Summary: Renewable generation of fuels using solar energy relies on the discovery of materials with durability and high solar-to-chemical conversion efficiency. This paper presents the high-throughput discovery of an amorphous Ni-Sb (1:1) oxide photoanode that meets the requirements of operational stability, visible photoresponse, and appreciable photovoltage. The lack of crystal anisotropy and operational stability of this amorphous photoanode open up new possibilities for photoelectrode development.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
E. A. Peterson, T. T. Debela, G. M. Gomoro, J. B. Neaton, G. A. Asres
Summary: This study investigates the structure and electronic properties of a vdW heterostructure consisting of Janus monolayer WSSe and monolayer ZnO. The effects of alignment, strain, orientation, and electric field on the dipole moments and band edge energies are examined. It is found that the out of plane dipole moment of the ZnO monolayer can be tuned by strain, allowing for a wide range of tuning of the heterostructure band edge energies. This study highlights the potential of strain-tunable 2D materials in controlling band offsets and alignment, with implications for clean energy applications.
Article
Physics, Multidisciplinary
Michele Kotiuga, Samed Halilov, Boris Kozinsky, Marco Fornari, Nicola Marzari, Giovanni Pizzi
Summary: Using first-principles molecular dynamics, we have discovered the persistence of intrinsic off-centerings in the cubic paraelectric phase of BaTiO3. These off-centerings are inconsistent with commonly used atomic-scale modeling methods. By employing systematic symmetry analysis, we have constructed representative structural models and defined energetically and dynamically stable prototypes. These findings are of significance for the computational engineering of functional materials.
PHYSICAL REVIEW RESEARCH
(2022)
