2019 New's Items

Non-Chemisorbed Gold-Sulfur Binding Prevails in Self-Assembled Monolayers

M. S. Inkpen
Z.-F. Liu
H. Li
L. M. Campos
J. B. Neaton
L. Venkataraman Nat
2019

Gold–thiol contacts are ubiquitous across the physical and biological sciences in connecting organic molecules to surfaces. When thiols bind to gold in self-assembled monolayers (SAMs) the fate of the hydrogen remains a subject of profound debate—with implications for our understanding of their physical properties, spectroscopic features and formation mechanism(s). Exploiting measurements of the transmission through a molecular junction, which is highly sensitive to the nature of the molecule–electrode contact, we demonstrate here that the nature of the gold–sulfur bond in SAMs can...

Observation of Moiré Excitons in WSe2/WS2 Heterostructure Superlattices

C. Jin
E. C. Regan
A. Yan
M. Iqbal Bakti Utama
D. Wang
S. Zhao
Y. Qin
S. Yang
Z. Zheng
S. Shi
K. Watanabe
T. Taniguchi
S. Tongay
A. Zettl
F. Wang
2019

Moiré superlattices enable the generation of new quantum phenomena in two-dimensional heterostructures, in which the interactions between the atomically thin layers qualitatively change the electronic band structure of the superlattice. For example, mini-Dirac points, tunable Mott insulator states and the Hofstadter butterfly pattern can emerge in different types of graphene/boron nitride moiré superlattices, whereas correlated insulating states and superconductivity have been reported in twisted bilayer graphene moiré superlattices...

First-Principles Approach to the Conductance of Covalently Bound Molecular Junctions

S. Refaely-Abramson
Z.-F. Liu
F. Bruneval
J. B. Neaton
2019

We develop a first-principles approach for accurate conductance calculations of covalently bound molecular junctions. Our approach extends the DFT+Σ method, an approximate GW-based self-energy correction scheme acting on a tractable molecular subspace (based on a gas-phase reference of the same dimension) that corrects level alignment in the junction relative to density functional theory (DFT). We introduce a new extended gas-phase reference system, consisting of the molecule and several lead atoms, whose frontier orbitals maximally project onto the conducting orbitals...

Gold Nanocrystal Etching as a Means of Probing the Dynamic Chemical Environment in Graphene Liquid Cell Electron Microscopy

Matthew R. Hauwiller
Justin C. Ondry
Cindy M. Chan
Prachi Khandekar
Jessica Yu
A. Paul Alivisatos
2019

Graphene liquid cell electron microscopy has the necessary temporal and spatial resolution to enable the in situ observation of nanoscale dynamics in solution. However, the chemistry of the solution in the liquid cell during imaging is as yet poorly understood due to the generation of a complex mixture of radiolysis products by the electron beam. In this work, the etching trajectories of nanocrystals were used as a probe to determine the effect of the electron beam dose rate and preloaded etchant, FeCl3, on the chemistry of the liquid cell. Initially,...

Communication: Rate constants in spatially inhomogenious systems

A.J. Schile
D.T. Limmer
2019

We present a theory and accompanying importance sampling method for computing rate constants in spatially inhomogenious systems. Using the relationship between rate constants and path space partition functions, we illustrate that the relative change in the rate of a rare event through space is isomorphic to the calculation of a free energy difference, albeit in a trajectory ensemble. Like equilibrium free energies, relative rate constants can be estimated by importance sampling. An extension to transition path sampling is proposed that combines biased path ensembles and weighted...

Layer-Dependent Electronic Structure of Atomically Resolved Two-Dimensional Gallium Selenide Telluride

Amin Azizi
Gabriel Antonius
Emma Regan
Rahmatollah Eskandar
Salman Kahn
Feng Wang
Steven G. Louie
Alex Zettl
2019

Alloying two-dimensional (2D) semiconductors provides a powerful method to tune their physical properties, especially those relevant to optoelectronic applications. However, as the crystal structure becomes more complex, it becomes increasingly difficult to accurately correlate response characteristics to detailed atomic structure. We investigate, via annular dark-field scanning transmission electron microscopy, electron energy loss spectroscopy, and second harmonic generation, the layered III–VI alloy GaSe0.5Te0.5 as a function of...

Frustrated supercritical collapse in tunable charge arrays on graphene

J. Lu
H-Z. Tsai
A. Tatan
S. Wickenburg
A. Omrani
D. Wong
A. Riss
E. Piatti
K. Watanabe
T. Taniguchi
A. Zettl
V. Pereira
M. Crommie
2019

The photon-like behavior of electrons in graphene causes unusual confinement properties that depend strongly on the geometry and strength of the surrounding potential. We report bottom-up synthesis of atomically-precise one-dimensional (1D) arrays of point charges on graphene that allow exploration of a new type of supercritical confinement of graphene carriers. The arrays were synthesized by arranging F4TCNQ molecules into a 1D lattice on back-gated graphene, allowing precise tuning of both the molecular charge and the array periodicity. While dilute arrays...

Solar-driven Carbon Dioxide Fixation using Photosynthetic Semiconductor Bio-hybrids

Stefano Cestellos-Blanco
Hao Zhang
Peidong Yang
2019

Solar-driven conversion of carbon dioxide to value-added carbon products is an ambitious objective of ongoing research efforts. However, high overpotential, low selectivity and poor CO2 mass transfer plague purely inorganic electrocatalysts. In this instance, we can consider a class of biological organisms that have evolved to achieve CO2 fixation. We can harness and combine the streamlined CO2 fixation pathways of these whole organisms with the exceptional...

Evidence of a Gate-Tunable Mott Insulator in a Trilayer Graphene Moiré Superlattice

Guorui Chen
Lili Jiang
Shuang Wu
Bosai Lv
Hongyuan Li
Kenji Watanabe
Takashi Taniguchi
Zhiwen Shi
Yuanbo Zhang
Feng Wang
2019

The Mott insulator is a central concept in strongly correlated physics and manifests when the repulsive Coulomb interaction between electrons dominates over their kinetic energy1,...

Observation of Highly Dispersive Bands in Pure Thin Film C60

D.W. Latzke
C. Ojeda-Aristizabal
S. M. Griffin
J. D. Denlinger
J. Neaton
A. Zettl
A. Lanzara
2019

While long-theorized, the direct observation of multiple highly dispersive C60 valence bands has eluded researchers for more than two decades due to a variety of intrinsic and extrinsic factors. Here we report a realization of multiple highly dispersive (330–520 meV) valence bands in pure thin film C60...