Homomorphic inference of deep neural networks for zero-knowledge verification of nuclear warheads.

Disarmament treaties have been the driving force towards reducing the large nuclear stockpile assembled during the Cold War. Further efforts are built around verification protocols capable of authenticating nuclear warheads while preventing the disclosure of confidential information. This type of problem falls under the scope of zero-knowledge protocols, which aim at multiple parties agreeing on a statement without conveying any information beyond the statement itself. A protocol capable of achieving all the authentication and security requirements is still not completely formulated. Here we propose a protocol that leverages the isotopic capabilities of NRF measurements and the classification abilities of neural networks. Two key elements guarantee the security of the protocol, the implementation of the template-based approach in the network's architecture and the use of homomorphic inference. Our results demonstrate the potential of developing zero-knowledge protocols for the verification of nuclear warheads using Siamese networks on encrypted spectral data.

Manipulation of Origin of Life Molecules: Recognizing Single-Molecule Conformations in ß-Carotene and Chlorophyll-a/ß-Carotene Clusters.

Carotenoids and chlorophyll are essential parts of plant leaves and are involved in photosynthesis, a vital biological process responsible for the origin of life on Earth. Here, we investigate how ß-carotene and chlorophyll-a form mixed molecular phases on a Au(111) surface using low-temperature scanning tunneling microscopy and molecular manipulation at the single-molecule level supported by density functional theory calculations. By isolating individual molecules from nanoscale molecular clusters with a scanning tunneling microscope tip, we are able to identify five ß-carotene conformations including a structure exhibiting a three-dimensional conformation. Furthermore, molecular resolution images enable direct visualization of ß-carotene/chlorophyll-a clsuters, with intimate structural details highlighting how they pair: ß-carotene preferentially positions next to chlorophyll-a and induces switching of chlorophyll-a from straight to several bent tail conformations in the molecular clusters.

Electron-phonon coupling in engineered magnetic molecules.

We probe the electron-phonon coupling for in situ engineered porphyrin-based magnetic molecular layers supported on weakly reactive surfaces. Using high-resolution scanning tunneling microscopy and spectroscopy at 4.5 K we show that the electronic and magnetic properties of the engineered molecules are the result of interplay between many-body spin-flip excitations and electron-phonon interactions.

Alkoxylated dehydrobenzo[12]annulene on Au(111): from single molecules to quantum dot molecular networks.

We demonstrate the effective confinement of surface electrons in the pores of molecular networks formed by dehydrobenzo[12]annulene (DBA) molecules with butoxy groups (DBA-OC4) on Au(111). Investigation of the network formation starting from single molecules reveals a considerable interaction of the molecules with the substrate, which is at the origin of the observed confinement.

Inducing magnetism in pure organic molecules by single magnetic atom doping.

We report on in situ chemical reactions between an organic trimesic acid (TMA) ligand and a Co atom center. By varying the substrate temperature, we are able to explore the Co-TMA interactions and create novel magnetic complexes that preserve the chemical structure of the ligands. Using scanning tunneling microscopy and spectroscopy combined with density functional theory calculations, we elucidate the structure and the properties of the newly synthesized complex at atomic or molecular size level. Hybridization between the atomic orbitals of the Co and the π orbitals of the ligand results in a delocalized spin distribution onto the TMA. The here demonstrated possibility to conveniently magnetize such versatile molecules opens up new potential applications for TMAs in molecular spintronics.

Probing the electronic properties of trimesic acid nanoporous networks on Au(111).

Nowadays molecular nanoporous networks have numerous uses in surface nanopatterning applications and in studies of host-guest interactions. Trimesic acid (TMA), a benzene derivative with three carboxylic groups, is a marvelous building block for forming 2D H-bonded porous networks. Here, we report a low-temperature study of the nanoporous "chicken-wire" superstructure formed by TMA molecules adsorbed on a Au(111) surface. Distinct preferential orientations of the porous networks on Au(111) lead to the formation of peculiar TMA polymorphs that are stabilized only at the boundary between rotational molecular domains. Scanning tunneling microscopy (STM) and spectroscopy are used to investigate the electronic properties of both the molecular building blocks and the pores. Sub-molecular-resolution imaging and spatially resolved electronic spectroscopy reveal a remarkable change in the appearance of the molecules in the STM images at energies in the range of the lowest unoccupied molecular orbital, accompanied by highly extended molecular wave functions into the pores. The electronic structure of the pores reflects a weak confinement of surface electrons by the TMA network. Our experimental observations are corroborated by density-functional-theory-based calculations of the nanoporous structure adsorbed on Au(111).

Polaronic transport and current blockades in epitaxial silicide nanowires and nanowire arrays.

Crystalline micrometer-long YSi2 nanowires with cross sections as small as 1 × 0.5 nm(2) can be grown on the Si(001) surface. Their extreme aspect ratios make electron conduction within these nanowires almost ideally one-dimensional, while their compatibility with the silicon platform suggests application as metallic interconnect in Si-based nanoelectronic devices. Here we combine bottom-up epitaxial wire synthesis in ultrahigh vacuum with top-down miniaturization of the electrical measurement probes to elucidate the electronic conduction mechanism of both individual wires and arrays of nanowires. Temperature-dependent transport through individual nanowires is indicative of thermally assisted tunneling of small polarons between atomic-scale defect centers. In-depth analysis of complex wire networks emphasize significant electronic crosstalk between the nanowires due to the long-range Coulomb fields associated with polaronic charge fluctuations. This work establishes a semiquantitative correlation between the density and distributions of atomic-scale defects and resulting current-voltage characteristics of nanoscale network devices.

Band gap narrowing of titanium oxide semiconductors by noncompensated anion-cation codoping for enhanced visible-light photoactivity.

"Noncompensated n-p codoping" is established as an enabling concept for enhancing the visible-light photoactivity of TiO2 by narrowing its band gap. The concept embodies two crucial ingredients: the electrostatic attraction within the n-p dopant pair enhances both the thermodynamic and kinetic solubilities, and the noncompensated nature ensures the creation of tunable intermediate bands that effectively narrow the band gap. The concept is demonstrated using first-principles calculations, and is validated by direct measurements of band gap narrowing using scanning tunneling spectroscopy, dramatically redshifted optical absorbance, and enhanced photoactivity manifested by efficient electron-hole separation in the visible-light region. This concept is broadly applicable to the synthesis of other advanced functional materials that demand optimal dopant control.

Realization of a four-step molecular switch in scanning tunneling microscope manipulation of single chlorophyll-a molecules.

Single chlorophyll-a molecules, a vital resource for the sustenance of life on Earth, have been investigated by using scanning tunneling microscope manipulation and spectroscopy on a gold substrate at 4.6 K. Chlorophyll-a binds on Au(111) via its porphyrin unit while the phytyl-chain is elevated from the surface by the support of four CH(3) groups. By injecting tunneling electrons from the scanning tunneling microscope tip, we are able to bend the phytyl-chain, which enables the switching of four molecular conformations in a controlled manner. Statistical analyses and structural calculations reveal that all reversible switching mechanisms are initiated by a single tunneling-electron energy-transfer process, which induces bond rotation within the phytyl-chain.

Nanoassembly of a fractal polymer: a molecular "Sierpinski hexagonal gasket".

Mathematics and art converge in the fractal forms that also abound in nature. We used molecular self-assembly to create a synthetic, nanometer-scale, Sierpinski hexagonal gasket. This nondendritic, perfectly self-similar fractal macromolecule is composed of bis-terpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Manipulating Kondo temperature via single molecule switching.

Two conformations of isolated single TBrPP-Co molecules on a Cu(111) surface are switched by applying +2.2 V voltage pulses from a scanning tunneling microscope tip at 4.6 K. The TBrPP-Co has a spin-active cobalt atom caged at its center, and the interaction between the spin of this cobalt atom and free electrons from the Cu(111) substrate can cause a Kondo resonance. Tunneling spectroscopy data reveal that switching from the saddle to a planar molecular conformation enhances spin-electron coupling, which increases the associated Kondo temperature from 130 to 170 K. This result demonstrates that the Kondo temperature can be manipulated just by changing molecular conformation without altering chemical composition of the molecule.

Manipulation of the Kondo effect via two-dimensional molecular assembly.

We report the manipulation of a Kondo resonance originating from the spin-electron interactions between a two-dimensional molecular assembly of TBrPP-Co molecules and a Cu(111) surface at 4.6 K. By manipulating nearest-neighbor molecules with a scanning tunneling microscope tip we are able to tune the spin-electron coupling of the center molecule inside a hexagonal molecular assembly in a controlled step-by-step manner. The Kondo temperature increases from 105 to 170 K with decreasing the number of nearest neighbor molecules from six to zero. The scattering of surface electrons by the molecules located at edges of the molecular layer reduces the spin-electron coupling strength for the molecules inside the layer. Investigations of different molecular arrangements indicate that the observed Kondo resonance is independent on the molecular lattice.