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DOE OSTI2026

Discovery of hydrogen storage molecules using large language models and machine learning

Accelerating the discovery of new molecules with targeted properties is a central challenge in molecular design. In this contribution, we present an AI-driven molecular discovery framework that integrates Large Language Models (LLMs) for generative molecular design with Machine Learning (ML)-based screening to identify novel Liquid Organic Hydrogen Carrier (LOHC) candidates. Using the developed framework, LOHC molecules were systematically generated, evaluated, and refined iteratively, combining LLM-guided molecular generation and ML-predicted hydrogenation enthalpies (Δ H ), under physicochemical property constraints such as optimal melting points (MP), desired hydrogen storage capacity (wt% H 2 ), and synthetic accessibility (SA) scores. This approach enabled the discovery of 42 new LOHC candidates in two distinct campaigns, one seeded with experimentally known and another with previously computationally identified LOHCs, respectively. Although we began with different numbers of starting molecules (31 vs . 7 seed molecules), both runs yielded a comparable number of viable candidates, suggesting an influence of chemically intuitive seed molecule selection for success. Selected LOHC molecules, such as 3-methyl pyridine, 1-ethylnapthalene, 1,1-diphenylethane, and benzofuran, were experimentally tested and compared with benchmark LOHCs (toluene and 9-ethylcarbazole) for hydrogenation using a series of commercial supported metal catalysts. The order of conversion into fully hydrogenated products at 200 °C was 3-methyl pyridine (100%) > 9-ethyl carbazole (86.4%) > 2,3-benzofuran (74%) > 1,1-diphenylethane (66.9%) > 1-ethylnapthalene (66.7%) > toluene (57%), further validating the AI-guided molecular design. This study demonstrates promise of LLM-driven molecular design in conjunction with ML-based screening for accelerated discovery and design of molecules.

Harb, Hassan [Argonne National Laboratory (ANL), A↗

DOE OSTI2013

Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7 cd/A and maximum power efficiency of 8.39 lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7 cd/A and 8.39 lm/W to 23 cd/A and 13.2 lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2016

Rotation mechanism of methylammonium molecules in organometal halide perovskite in cubic phase: An ab initio molecular dynamics study

Rotation of methylammonium (CH 3 NH 3 or MA) molecules is believed to govern the excellent transport properties of photocarriers in the MA lead iodide (MAPbI 3 ) perovskite. Of particular interest is its cubic phase, which exists in industrially important films at room temperature. In order to investigate the rotational behaviors of the MA molecules, we have performed ab initio molecular dynamics simulations of cubic-MAPbI 3 at room temperature. There are two types of rotational motions of MA molecules in a crystalline PbI 3 cage: reorientation of a whole molecule and intramolecular rotation around the C–N bond within MA molecules. Using a cubic symmetry-assisted analysis (CSAA), we found that the prominent orientation of the C–N bond is the crystalline ❬110❭directions, rather than the ❬100❭ and ❬111❭ directions. Rapid rotation around the C–N bond is also observed, which easily occurs when the rotational axis is parallel to the ❬110❭ directions according to the CSAA. To explain the atomistic mechanisms underlying these CSAA results, we have focused on the relation between H–I hydrogen bonds and the orientation of an MA molecule. Here, the hydrogen bonds were defined by population analysis, and it has been found that, while H atoms in the CH 3 group (HC) hardly interacts with I atoms, those in the NH3 group (HN) form at least one hydrogen bond with I atoms and their interatomic distances are in a wide range, 2.2–3.7 Å. Based on these findings, we have given a possible explanation to why the ❬110❭ directions are preferred. Namely, the atomic arrangement and interatomic distance between MA and surrounding I atoms are most suitable for the formation of hydrogen bonds. In addition to films, these results are potentially applicable to the rotational behaviors in bulk MAPbI 3 as well, considering that the atomistic structure and time constants regarding the rotation of MA molecules statistically agree with bulk experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

The ratio of the number of states in asymmetric and symmetric ozone molecules deviates from the statistical value of 2

Accurate calculations of vibrational states in singly and doubly substituted ozone molecules are carried out, up to dissociation threshold. Analysis of these spectra reveals noticeable deviations from the statistical factor of 2 for the ratio between the number of states in asymmetric and symmetric ozone molecules. It is found that, for the lower energy parts of spectra, the ratio is less than 2 in the singly substituted ozone molecules, but it is more than 2 in the doubly substituted ozone molecules. However, the upper parts of spectra, just below dissociation thresholds, exhibit a different behavior. In this energy range, the singly and doubly substituted ozone molecules behave similar, with the ratio of states in asymmetric and symmetric ozone molecules being more than 2 in both cases. Here, this property may contribute to an explanation of the mysterious η-effect in the ozone forming reaction that favors the formation of the asymmetric ozone molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

An evaluation for geometries, formation enthalpies, and dissociation energies of diatomic and triatomic (C, H, N, O), NO 3 , and HNO 3 molecules from the PAW DFT method with PBE and optB88-vdW functionals

The structural geometries, formation enthalpies, and dissociation energies of all diatomic and triatomic molecules consisting of the four basic elements C, H, N, and/or O are calculated using the projector augmented wave density functional theory (DFT) method with the Perdew–Burke–Ernzerhof and optB88-vdW exchange-correlation functionals. The calculations are also extended to two larger molecules NO 3 and HNO 3 , which consist of four and five atoms, respectively. In total, 82 molecules or isomers are considered in the calculations. The geometric parameters including 42 bond lengths and 15 bond angles of these molecules calculated using the planewave DFT method are highly satisfactory, relative to the available experimental data. The error analysis is also performed for 49 formation enthalpies and 138 dissociation energies (including 51 atomization energies as well as the corresponding bond dissociation energies). The results are also compared with the previous data from various atomic-orbital-based methods for molecules and from similar or different planewave DFT methods for various solids and other molecules. This provides an informative and instructive evaluation especially for calculating the large-size material systems containing these small molecules as well as for developing the DFT methods further.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2014

Structure and dynamics of C60 molecules on Au(111)

Earlier studies of C60 adsorption on Au(111) reported many interesting and complex features. We have performed coordinated low-energy electron diffraction, scanning tunneling microscopy (STM), and density functional theory studies to elucidate some of the details of the monolayer commensurate (2√3 × 2√3)R30° phase. We have identified the adsorption geometries of the two states that image as dim and bright in STM. These consist of a C60 molecule with a hexagon side down in a vacancy (hex-vac) and a C60 molecule with a carbon-carbon 6:6 bond down on a top site (6:6-top), respectively. We have studied the detailed geometries of these states and find that there is little distortion of the C60 molecules, but there is a rearrangement of the substrate near the C60 molecules. The two types of molecules differ in height, by about 0.7 Å, which accounts for most of the difference in their contrast in the STM images. The monolayer displays dynamical behavior, in which the molecules flip from bright to dim, and vice versa. We interpret this flipping as the result of the diffusion of vacancies in the surface layers of the substrate. Our measurements of the dynamics of this flipping from one state to the other indicate that the activation energy is 0.66 ± 0.03 eV for flips that involve nearest-neighbor C60 molecules, and 0.93 ± 0.03 for more distant flips. Based on calculated activation energies for vacancies diffusing in Au, we interpret these to be a result of surface vacancy diffusion and bulk vacancy diffusion. These results are compared to the similar system of Ag(111)-(2√3 × 2√3)R30°-C60. In both systems, the formation of the commensurate C60 monolayer produces a large number of vacancies in the top substrate layer that are highly mobile, effectively melting the interfacial metal layer at temperatures well below their normal melting temperatures.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Intra-molecular coupling within double-segmented molecules impacting magnetic tunnel junction-based molecular spintronics devices

The intra-molecular coupling within multiple units of paramagnetic molecules can produce various effects on molecular spintronics devices (MSD). Here, this paper focuses on double-segmented molecules as the device element to advance understanding of the Impact of internal molecular structure on magnetic tunnel junction-based MSD (MTJMSD). We performed Monte Carlo simulations (MCS) to fill the knowledge gap about the intramolecular coupling role in the magnetic properties of the MTJMSD. This study explored a double-segmented molecule containing two atomic sections, each with a net spin state interacting via Heisenberg exchange coupling within molecules and with ferromagnetic electrodes at different thermal energies, magnetic fields, and coupling strengths. This study also investigated the effect of magnetic field on the double-segmented molecule-based cross-junction-shaped MTJMSD. We also compared the effect of the magnetic field on the mono and double-segmented molecules when connected to two ferromagnetic electrodes. In the strong coupling regime, the intramolecular coupling and molecule coupling with the two ferromagnetic electrodes dominated the MTJMSD response near the molecular junction area. This study provides insight for evaluating the impact of molecular nanostructure internal connectedness on the integrated MSD.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Dynamics of Activated Molecules

Experimental studies have been performed to investigate the collisional energy transfer processes of gas-phase molecules that contain large amounts of internal energy. Such molecules are prototypes for molecules under high temperature conditions relevant in combustion and information about their energy transfer mechanisms is needed for a detailed understanding and modeling of the chemistry. We use high resolution transient IR absorption spectroscopy to measure the full, nascent product distributions for collisions of small bath molecules that relax highly vibrationally excited pyrazine molecules with E=38000 cm-1 of vibrational energy. To perform these studies, we developed new instrumentation based on modern IR light sources to expand our experimental capabilities to investigate new molecules as collision partners. This final report describes our research in four areas: the characterization of a new transient absorption spectrometer and the results of state-resolved collision studies of pyrazine(E) with HCl, methane and ammonia. Through this research we have gained fundamental new insights into the microscopic details of relatively large complex molecules at high energy as they undergo quenching collisions and redistribute their energy.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2023

Space-Time Quantum Information from the Entangled States of Magnetic Molecule (STI Product)

This collaborative project combines synthesis, measurement, and theory by three faculty members at the Eddleman Quantum Institute of UC Irvine to effectively investigate the quantum properties of molecules in the space, time, and frequency domains. Through synthetic chemistry, molecules are tailored for their magnetic and coherent properties. By combining femtosecond (fs) terahertz (THz) light and a continuous wave (cw) THz laser with a low temperature scanning tunneling microscope (STM), quantum phenomena are probed with simultaneous femtosecond temporal and atomic-scale spatial resolution. In particular, the invention of the quantum superposition microscope (QSM) advances quantum sensing for enhanced spectroscopy and imaging capabilities. Coupling theory to the experimental efforts offers a deeper understanding and predictive power for the molecular systems. The phenomena of superposition, entanglement, and coherence is central to quantum information science and can be realized in qubit states. Many systems can be modeled by a double-well potential in which two levels are formed in the two lowest energy states interacting with the environment and external radiation. In focusing on molecules as two-level systems, the underlying expectation is that their tunable composition and structure allows an effective parameter space to optimize their use as qubits for quantum sensing and computing. The THz radiation induces the superposition between the two states, appearing as temporal oscillations that damp in amplitude. Enhanced spectroscopy and imaging in the time and frequency domains is achieved through the extreme sensitivity of the frequency and damping of coherence of two-level systems to its environment. A single hydrogen molecule trapped in the STM tunneling gap experiences a double-well potential and absorption of THz femtosecond pulses of light creates the superposition of its two levels, appearing as damped oscillations in the light induced direct current (DC). The oscillation frequency depends sensitively on the electric field distribution of the copper nitride (Cu 2 N) surface, through the Stark effect, and associated with the different charge distributions at the copper and nitrogen sites and in between. This QSM can resolve variation in the surface electric field with 0.02 nanometer resolution. In addition, the single hydrogen molecule entaes with nearby hydrogen molecules as seen in the avoided level crossings of energy (oscillation frequency) versus the voltage across the tunneling gap. Thus, the first application of the QSM senses and images the surface electric field at the atomic scale. Results from this project advance fundamental understanding of quantum phenomena, develop novel synthesis, measurement, and theory, provide the knowledge foundation for molecule-based qubits and sensing that enable the development of the QSM and emergent technologies. This project trained researchers in quantum information science, extended knowledge in classrooms, and outreached to the community.

47 OTHER INSTRUMENTATION↗

NASA NTRS1989

Angular motion of a PAH molecule in interstellar environment

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Rouan, D.↗

NASA NTRS1992

Comets as a possible source of prebiotic molecules

Prebiotic molecules derive from abiotic organic molecules, radicals, and ions that pervade the universe at temperatures as high as several 1000 K. Here we review the role of organic molecules that condensed at low temperatures before or during comet formation in the early history of the Solar System. Recent spacecraft encounters and ground-based observations of carbon-rich volatile and dust components of comet comae provide a broad database for the investigation of these organic molecules. New laboratory data for some potential cometary organics are presented. Probable icy organic constituents of the nucleus and CHON particles as likely candidates for the distributed sources of gas-phase organic species in the coma are discussed. There is broad agreement that many organic molecules observed in the coma originate from the dust that must have existed in the solar nebula at the time and place of comet formation. We conclude that complex organic molecules found in comets may be a source of prebiotic molecules that led to the origins of life.

Huebner, W. F.↗

NASA NTRS1995

Complex molecules in Sagittarius B2(N): The importance of grain chemistry

The complex molecules vinyl cyanide (CH2CHCN), methyl formate (HCOOCH3), and ethyl cyanide (CH3CH2CN) were observed in the Sgr B2 star-forming region with the BIMA millimeter wavelength array. A region with diameter less than 0.1 pc toward the Sgr B2(N) molecular core is found to be the major source of these molecules. Also, this source is coincident with continuum emission from dust and a center of H2O maser activity. Ultracompact (UC) H 11 regions are located within 0.1 pc. Strikingly, none of these molecules is detected toward Sgr B2(M), a core located 1 minute south of Sgr B2(N). The existence of complex molecules, a large mass of dust, high-velocity H2O masers, and UC H 11 regions strongly suggests that the Sgr B2(N) region has just begun to form stars, while the absence of strong dust emission and large molecules suggests Sgr B2(M) is more evolved. The detection of large molecules coincident with continuum emission from dust supports the idea found in current chemical models that grain chemistry is of crucial importance for the formation of these molecules.

Miao, Yanti↗

NASA NTRS1999

Exotic Molecules in Space: A Coordinated Astronomical Laboratory and Theoretical Study

The past three years have been a period of great progress in our laboratory investigation of molecules of astrophysical interest-the most productive by far in the 20-year history of a research program which has led to the discovery of over 20% of the 123 known interstellar and circumstellar molecules. Most of the discoveries made during this period have been the result of the construction in late 1995 and early 1996 of a Fourier transform microwave spectrometer working in the centimeter-wave band. The sensitivity of this instrument from the moment that it was turned on has exceeded our expectations by an order of magnitude. The Table below shows the 46 new molecules which have been discovered. Most are carbon chains, the dominant type of molecule which has been found in space. Several comments with respect to these molecules should be made: 1. There are probably no mistakes in any of the identifications, since these have been confirmed by the standard, powerful assays and tests used to check spectroscopic identifications: isotopic substitution, quantum calculations of the expected molecular structures, detection of hyperfine structure, Zeeman effect, etc. 2. The radio laboratory astrophysics of the entire set is complete for the time being, in the sense that essentially all the astronomically interesting radio transitions (including hfs when present) are either directly measured or can now be calculated from the derived spectroscopic constants to better than 1 part per million (or 0.3 km s-1 in radial velocity, and often much better than that). 3. Six of the forty six new molecules have already been identified in space, in every case but one on the basis of our laboratory measurements. 4. Sensitive as they are, our laboratory techniques are far from fundamental limits on sensitivity, and 5. One of the principal motivations of our research is to close the fairly small mass and size gap, now only a factor of a few, between the smallest postulated interstellar grains and the largest identified interstellar molecules.

Thaddeus, Patrick↗

NASA NTRS1995

Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

Huo, Winifred M.↗

NASA NTRS2010

The Origins and Evolution of Molecules in Icy Solids

Astronomical observations of the past few decades have revealed the existence of a variety of molecules in extraterrestrial ices. These molecules include H2O, CO, and CO2, and organics such as CH4, CH30H, and C2H6. Some ices are dominated by polar molecules, while non-polar species appear to dominate others. Observations, mainly in the radio and IR regions, have allowed the inference of other solid-phase molecules whose formation remains difficult to explain by gas-phase chemistry alone. Several laboratory research groups have reported on extensive experiments on the solid-phase reaction chemistry of icy materials, generally as initiated by either ionizing radiation or vacuum-UV photons. These experiments not only permit molecular identifications to be made from astronomical observations, but also allow predictions of yet unidentified molecules. This laboratory approach has evolved over more than 30 years with much of the earliest work focusing on complex mixtures thought to represent either cometary or interstellar ices. Although those early experiments documented a rich solid-state photo- and radiation chemistry, they revealed few details of reactions for particular molecules, partly due to the multi-component nature of the samples. Since then, model systems have been examined that allow the chemistry of individual species and specific reactions to be probed. Reactions involving most of the smaller astronomical molecules have now been studied and specific processes identified. Current laboratory work suggests that a variety of reactions occur in extraterrestrial ices, including acid-base processes, radical dimerizations, proton transfers, oxidations, reductions, and isomerizations. This workshop presentation will focus on chemical reactions relevant to solar system and interstellar ices. While most of the work will be drawn from that to which the speaker has contributed, results from other laboratories also will be included. Suggestions for future studies will be made, with an emphasis on some present deficiencies. The speaker's work has been generously supported by these NASA research programs: Cassini Data Analysis, Exobiology, Mars Fundamental Research, Outer Planets Research, Planetary Atmospheres, Planetary Geology and Geophysics, and the NASA Astrobiology Institute.

Hudson, Reggie L.↗

DOE OSTI2016

Single-Molecule Fluorescence Imaging for Studying Organic, Organometallic, and Inorganic Reaction Mechanisms

The reactive behavior of individual molecules is seldom observed, because we usually measure the average properties of billions of molecules. What we miss is important: the catalytic activity of less than 1% of the molecules under observation can dominate the outcome of a chemical reaction seen at a macroscopic level. Currently available techniques to examine reaction mechanisms (such as nuclear magnetic resonance spectroscopy and mass spectrometry) study molecules as an averaged ensemble. These ensemble techniques are unable to detect minor components (under ~1%) in mixtures or determine which components in the mixture are responsible for reactivity and catalysis. In the field of mechanistic chemistry, there is a resulting heuristic device that if an intermediate is very reactive in catalysis, it often cannot be observed (termed “Halpern’s Rule” ). Ultimately, the development of single-molecule imaging technology could be a powerful tool to observe these “unobservable” intermediates and active catalysts. Single-molecule techniques have already transformed biology and the understanding of biochemical processes. The potential of single-molecule fluorescence microscopy to address diverse chemical questions, such as the chemical reactivity of organometallic or inorganic systems with discrete metal complexes, however, has not yet been realized. In this respect, its application to chemical systems lags significantly behind its application to biophysical systems. This transformative imaging technique has broad, multidisciplinary impact with the potential to change the way the chemistry community studies reaction mechanisms and reactivity distributions, especially in the core area of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Department of Energy Project DE-SC0012198: Probing Electron-Molecule Scattering with HHG: Theory and Experiment (Final Report)

The study of the motion of atoms in molecules is important to understanding many areas of physical and life sciences. Such motion occurs on many different times scales, with electronic motion occurring on a sub-femtosecond time scale, and simple vibrational motion in tens to hundreds of femtoseconds. One way to follow such processes in real time is by the use of shortpulsed lasers, and in particular by studying time-resolved photoionization and the related process of high-harmonic generation (HHG). Thus there has been much effort to develop the tools necessary to probe molecular systems using short pulse lasers and understanding the sensitivity of the different possible probes to the time dependent geometric structure as well as the electronic structure of molecules. Our research has particularly focused on the connection between high-field processes and the more traditional weak field photoionization processes. Strong field and weak field processes can be connected through models that involve the same matrix elements. We have demonstrated in our study of HHG from SF 6 that the spectrum is sensitive to the interplay between the angular dependence of the ionization step and recombination step. In our study of rescattering spectroscopy, we have shown that with a combination of experiment and theory, we can use this high-field spectroscopy to determine molecular structure in molecules such as C 2 H 4 . We have also developed new computational tools based on overset grids to enable studies on larger molecular systems which use much more robust numerical approaches so that the resulting code can be a tool that non-specialists can use to study related systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Anisotropic Conductivity at the Single-Molecule Scale

In most junctions built by wiring a single molecule between two electrodes, the electrons flow along only one axis: between the two anchoring groups. However, molecules can be anisotropic, and an orientation-dependent conductance is expected. Here, we fabricated single-molecule junctions by using the electrode potential to control the molecular orientation and access individual elements of the conductivity tensor. We measured the conductance in two directions, along the molecular plane as the benzene ring bridges two electrodes using anchoring groups (upright) and orthogonal to the molecular plane with the molecule lying flat on the substrate (planar). The perpendicular (planar) conductance is about 400 times higher than that along the molecular plane (upright). Overall, this offers a new method for designing a reversible room-temperature single-molecule electromechanical switch that controllably employs the electrode potential to orient the molecule in the junction in either “ON” or “OFF” conductance states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗