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In this review we discuss the interaction of a molecular excited state with a smooth substrate. Both theoretical and experimental work is treated. This discussion will concentrate on the classical treatment of the interaction because of its astounding success in comparison with experiment. We do however discuss the shortcomings of the classical treatment and some recent approaches to correcting these limitations. The experimental work is considered in detail but we focus on the region close to the substrate, less than 500 Å away because the longer distance regime has been well reviewed. At the end of this article we briefly point out areas where future work is needed. © 1985.

The distance dependent lifetime of biacetyl separated from a Ag(111) crystal by NH3 spacer layers ranging in thickness from 28 to 457 Å has been measured. We extended previous work, where the molecular emission was resonant with the silver interband/plasmon transition, to the case where the emission is below the interband transition. The modulation of the radiative rate is described inadequately by the classical theory for our experimental geometry. At short distances where nonradiative energy transfer to the metal is important, the classical prediction deviates from the data as well. These observations are consistent with a model in which energy is transferred to electrons localized at the metal surface but might also be explained by an inability of the classical theory to model the radiative rate properly. © 1985 American Institute of Physics.

The fluorescence decays from submonolayers of pyrene separated from Si(111) by Xe spacer layers are measured as a function of spacer thickness (17-200 Å), pyrene coverage, and emission wavelength. The results are explained in terms of two decay channels: energy transfer and trapping among the molecules in the two-dimensional pyrene overlayer, and excitation of electrons from the valence to the conduction band in the Si(111) by the dipole near field of the electronically excited pyrene molecule. The intralayer energy transfer is modeled using the Kohlrausch equation N(t)=N0 exp(-t/tau;) α, in which α is related to the distribution of pyrene molecules in energy. Energy transfer from the molecule to the semiconductor is modeled using the classical image dipole theory. The classical model is used to calculate the energy transfer rates from a dipole to Si and GaAs as a function of dipole-semiconductor separation, and as a function of dipole emission wavelength. © 1987 American Institute of Physics.

Chiral perovskites have emerged as a new class of nanomaterials for manipulation and control of spin polarized current and circularly polarized light for applications in spintronics, chiro-optoelectronics, and chiral photonics. While significant effort has been made in discovering and optimizing strategies to synthesize different forms of chiral perovskites, the mechanism through which chirality is imbued onto the perovskites by chiral surface ligands remains unclear. In this minireview, we provide a detailed discussion of one of the proposed mechanisms, electronic imprinting from a chiral ligand.

The oxygen evolution reaction (OER) remains an important bottleneck for widespread implementation of a hydrogen economy. While improvements in the OER can be realized by spin polarizing the reaction intermediates, these methods often rely on applying external magnetic fields to ferromagnetic catalysts or by adsorbing chiral molecules onto the catalyst. Here, we show that the addition of chiral additives to the conductive binder supporting the catalysts enhances the selectivity for O 2 formation and results in exceedingly high mass activities. The results are explained within the context of a statistical model in which the additives are hypothesized to act as a localized chiral bias that enhances radical intermediate coupling. More broadly, these studies illustrate a flexible design motif for improving OER catalysis that persists under different pH conditions, is independent of the choice of catalyst, and can be extrapolated to other chemical reactions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Electron transfer (eT) processes have garnered the attention of chemists and physicists for more than seven decades, and it is commonly believed that the essential features of the electron transfer mechanism are well understood─despite some open questions relating to the efficiency of long-range eT in some systems and temperature effects that are difficult to reconcile with the existing theories. The chiral induced spin selectivity (CISS) effect, which has been studied experimentally since 1999, demonstrates that eT through chiral systems depends on the electron's spin. Attempts to explain the CISS effect by adding spin-orbit coupling to the existing eT theories fails to reproduce the experimental results quantitatively, and it has become evident that the theory for explaining CISS must consider electron-vibration and/or electron-electron interactions. In this Perspective we identify some features of the CISS effect that imply that we should reconsider and refine the Marcus-Levich-Jortner mechanistic description for eT processes, especially for nonlinear systems and in the case of long-range eT.

This review discusses opportunities in chemistry that are enabled by the chiral induced spin selectivity (CISS) effect. First, the review begins with a brief overview of the seminal studies on CISS. Next, we discuss different chiral material systems whose properties can be tailored through chemical means, with a special emphasis on hybrid organic-inorganic layered materials that exhibit some of the largest spin filtering properties to date. Then, we discuss the promise of CISS for chemical reactions and enantioseparation before concluding., (© The Author(s) 2024. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd.)

This study presents a halide exchange mediated cation exchange reaction to co-dope d- and f-block elements in CsPbX 3 NPs at room temperature. Addition of MnCl 2 and YbCl 3 to CsPbBr 3 NPs induces ion exchange reactions generating the corresponding CsPbBr 3 /MnCl 2 YbCl 3 NPs. In addition to the perovskite emission, the NPs display sensitized Mn 2+ and Yb 3+ emissions in concert spanning the UV, visible, and NIR spectral region. Structural and spectroscopic characterizations indicate a substitutional displacement of Pb 2+ by the Mn 2+ and Yb 3+ . The identity of the host halide in modulating the ion exchange reactions was also tested. An effective perovskite host NP is presented that can be used to incorporate d-f or f-f dopant combinations to realize a gamut of dopant emission lines. A charge trapping based photophysical model is developed that focuses on rational energy alignments to predict dopant emissions semi-empirically and aids the design of optimal perovskite host-multi-dopant combinations.

The chiral induced spin selectivity (CISS) effect, in which the structural chirality of a material determines the preference for the transmission of electrons with one spin orientation over that of the other, is emerging as a design principle for creating next-generation spintronic devices. CISS implies that the spin preference of chiral structures persists upon injection of pure spin currents and can act as a spin analyzer without the need for a ferromagnet. Here, we report an anomalous spin current absorption in chiral metal oxides that manifests a colossal anisotropic nonlocal Gilbert damping with a maximum-to-minimum ratio of up to 1000%. A twofold symmetry of the damping is shown to result from differential spin transmission and backscattering that arise from chirality-induced spin splitting along the chiral axis. These studies reveal the rich interplay of chirality and spin dynamics and identify how chiral materials can be implemented to direct the transport of spin current.

Covalent bonding interactions determine the energy-momentum ( E - k ) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the E - k dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to-semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV., Competing Interests: Competing interests statement:The authors declare no competing interest.

Since the initial landmark study on the chiral induced spin selectivity (CISS) effect in 1999, considerable experimental and theoretical efforts have been made to understand the physical underpinnings and mechanistic features of this interesting phenomenon. As first formulated, the CISS effect refers to the innate ability of chiral materials to act as spin filters for electron transport; however, more recent experiments demonstrate that displacement currents arising from charge polarization of chiral molecules lead to spin polarization without the need for net charge flow. With its identification of a fundamental connection between chiral symmetry and electron spin in molecules and materials, CISS promises profound and ubiquitous implications for existing technologies and new approaches to answering age old questions, such as the homochiral nature of life. This review begins with a discussion of the different methods for measuring CISS and then provides a comprehensive overview of molecules and materials known to exhibit CISS-based phenomena before proceeding to identify structure-property relations and to delineate the leading theoretical models for the CISS effect. Next, it identifies some implications of CISS in physics, chemistry, and biology. The discussion ends with a critical assessment of the CISS field and some comments on its future outlook.

This work presents a spectroscopic and photocatalytic comparison of water splitting using yttrium iron garnet (Y 3 Fe 5 O 12 , YIG) and hematite (α-Fe 2 O 3 ) photoanodes. Despite similar electronic structures, YIG significantly outperforms widely studied hematite, displaying more than an order of magnitude increase in photocurrent density. Probing the charge and spin dynamics by ultrafast, surface-sensitive XUV spectroscopy reveals that the enhanced performance arises from (1) reduced polaron formation in YIG compared to hematite and (2) an intrinsic spin polarization of catalytic photocurrents in YIG. Ultrafast XUV measurements show a reduction in the formation of surface electron polarons compared to hematite due to site-dependent electron-phonon coupling. This leads to spin polarized photocurrents in YIG where efficient charge separation occurs on the T d sub-lattice compared to fast trapping and electron/hole pair recombination on the O h sub-lattice. These lattice-dependent dynamics result in a long-lived spin aligned hole population at the YIG surface, which is directly observed using XUV magnetic circular dichroism. Comparison of the Fe M 2,3 and O L 1 -edges show that spin aligned holes are hybridized between O 2p and Fe 3d valence band states, and these holes are responsible for highly efficient, spin selective water oxidation by YIG. Together, these results point to YIG as a new platform for highly efficient, spin selective photocatalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Chiral perovskite nanoparticles and films are promising for integration in emerging spintronic and optoelectronic technologies, yet few design rules exist to guide the development of chiral material properties. The chemical space of potential building blocks for these nanostructures is vast, and the mechanisms through which organic ligands can impart chirality to the inorganic perovskite lattice are not well understood. In this work, we investigate how the properties of chiral ammonium ligands, the most common organic ligand type used with perovskites, affect the circular dichroism of strongly quantum confined CsPbBr 3 nanocrystals. We show that aromatic ammonium ligands with stronger electron-donating groups lead to higher-intensity circular dichroism associated with the lowest-energy excitonic transition of the perovskite nanocrystal. We argue that this behavior is best explained by a modulation of the exciton wavefunction overlap between the nanocrystal and the organic ligand, as the functional groups on the ligand can shift electron density toward the organic species-perovskite lattice interface to increase the imprinting., (© 2024. The Author(s).)

We discuss the possibility of using circularly polarized luminescence (CPL) as a tool to probe individual triplet spin sublevels that are populated nonadiabatically following photoexcitation. This study is motivated by a mechanism proposed for chirality-induced spin selectivity in which coupled electronic-nuclear dynamics may lead to a non-statistical population of the three triplet sublevels in chiral systems. We find that low-temperature CPL should aid in quantifying the exact spin state/s populated through coupled electronic-nuclear motion in chiral molecules., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

High-nickel layered oxides, e.g., LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), are promising candidates for cathode materials in high-energy-density lithium-ion batteries (LIBs). Complementing the notable developments of modification of active materials, this study focused on the polymer binder materials, and a new synthetic route was developed to engineer PVDF binders by covalently grafting copolymers from poly(vinylidene fluoride- co -chlorotrifluoroethylene) (PVDF-CTFE) with multiple functionalities using atom transfer radical polymerization (ATRP). The grafted random copolymer binder provided excellent flexibility (319% elongation), adhesion strength (50 times higher than PVDF), transition metal chelation capability, and efficient ionic conductivity pathways. The NCM811 half-cells using the designed binders exhibited a remarkable rate capability of 143.4 mA h g -1 at 4C and cycling stability with 70.1% capacity retention after 230 cycles at 0.5 C, which is much higher than the 52.3% capacity retention of nonmodified PVDF. The well-retained structure of NCM811 with the designed binder was systematically studied and confirmed by post-mortem analysis., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

This work shows that electron spin polarization and stereoisomeric effects make comparable contributions to the enantioselective binding of amino acids. Magneto-electrochemical quartz crystal microbalance methods are used to study the adsorption of chiral amino acids onto a monolayer film of chiral molecules that are spin polarized by an underlying ferromagnetic substrate. The direction of the electron spin polarization affects both the kinetics and thermodynamics of the enantiospecific adsorption of the amino acids. Comparison of these data with the circular dichroism (CD) spectra of the amino acid adsorbates shows that the CD spectrum of the interacting group provides a good figure-of-merit for predicting the contributions of electron spin to the intermolecular interaction. These findings demonstrate the importance of electron spin in enantioselective intermolecular interactions between chiral amino acids and represent a paradigm shift for how selectivity should be viewed in biorecognition.

Protein voltammetry studies of cytochrome c , immobilized on chiral tripeptide monolayer films, reveal the importance of the electron spin and the film's homochirality on electron transfer kinetics. Magnetic film electrodes are used to examine how an asymmetry in the standard heterogeneous electron transfer rate constant arises from changes in the electron spin direction and the enantiomer composition of the tripeptide monolayer; rate constant asymmetries as large as 60% are observed. These findings are rationalized in terms of the chiral induced spin selectivity effect and spin-dependent changes in electronic coupling. Lastly, marked differences in the average rate constant are shown between homochiral ensembles, in which the peptide and protein possess the same enantiomeric form, compared to heterochiral ensembles, where the handedness of the peptide layer is opposite to that of the protein or itself comprises heterochiral building blocks. These data demonstrate a compelling rationale for why nature is homochiral; namely, spin alignment in homochiral systems enables more efficient energy transduction.

This work uses magneto-electrochemical quartz crystal microbalance methods to study the enantiospecific adsorption of chiral molecules onto a ferromagnetic substrate. The effects of solution conditions, pH, and solvent isotope composition indicate that the kinetics of the enantiomeric adsorption depend strongly on the charge state and geometry of the adsorbate, whereas no thermodynamic contributions to enantiospecificity are found. Density functional theory calculations reveal that an interplay between the adsorbate and solvent molecules is important for defining the observed enantiospecific preference with an applied magnetic field; however, it remains unclear if intermolecular vibrational couplings contribute to the phenomenon., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The adsorption of oxidatively damaged DNA onto ferromagnetic substrates was investigated. Both confocal fluorescence microscopy and quartz crystal microbalance methods show that the adsorption rate and the coverage depend on the magnetization direction of the substrate and the position of the damage site on the DNA relative to the substrate. SQUID magnetometry measurements show that the subsequent magnetic susceptibility of the DNA-coated ferromagnetic film depends on the direction of the magnetic field that was applied to the ferromagnetic film as the molecules were adsorbed. This study reveals that (i) the spin and charge polarization in DNA molecules is changed significantly by oxidative damage in the G bases and (ii) the rate of adsorption on a ferromagnet, as a function of the direction of the magnetic dipole of the surface, can be used as an assay to detect oxidative damage in the DNA.

Continual progress in technologies that rely on water splitting are often hampered by the slow kinetics associated with the oxygen evolution reaction (OER). Here, we show that the efficiency of top-performing catalysts can be improved, beyond typical thermodynamic considerations, through control over reaction intermediate spin alignment during electrolysis. Spin alignment is achieved using the chiral induced spin selectivity (CISS) effect and the improvement in OER manifests as an increase in Faradaic efficiency, decrease in reaction overpotential, and change in the rate determining step for chiral nanocatalysts over compositionally analogous achiral nanocatalysts. These studies illustrate that a defined spatial orientation of the nanocatalysts is not necessary to exhibit spin selectivity and therefore represent a viable platform for employing the transformative role of chirality in other reaction pathways and processes., (© 2023. The Author(s).)

Chiral metal halide perovskites have garnered substantial interest because of their promising properties for application in optoelectronics and spintronics. Understanding the mechanism of chiral imprinting is paramount for optimizing their utility. To elucidate the nature of the underlying chiral imprinting mechanism, we investigated how the circular dichroism (CD) intensity varies with nanoparticle size for quantum confined sizes of colloidal CsPbBr 3 perovskite nanoparticles (NPs) capped by chiral β-methylphenethylammonium bromide ligands. We find that the CD intensity decreases strongly with increasing NP size, which, along with the shape of the CD spectra, points to electronic interactions between ligand and NP as the dominant mechanism of chiral imprinting in smaller NPs. We observe that as the NP size increases and crosses the quantum confinement threshold, the dominant mechanism of chirality transfer switches and is dominated by surfaces effects, e.g. , structural distortions. These findings provide a benchmark for quantitative models of chiral imprinting.

Motivated by experiments which display unusual length and temperature effects for electron transfer in the nanometer length regime, we propose a new approach for describing long-range electron transfer (ET) processes through molecules. We posit that the electron reorganization in the molecules (e.g., the electronic polarization of a macromolecule or organic film by an applied electric potential, or the injected charge generating a dipole moment) should be included in the description. We numerically solve a one-dimensional model for the electron transport, which includes electron-electron interactions explicitly, and we show that it generates a power law distance dependence for electron transport similar to that observed in experiments. The model does not include vibrations explicitly and should be consistent with the weak temperature dependences observed experimentally. This approach emphasizes the need to treat the electronic changes in the molecule(s) more explicitly to understand the behavior.

The chirality-induced spin selectivity (CISS) effect facilitates a paradigm shift for controlling the outcome and efficiency of spin-dependent chemical reactions, for example, photoinduced water splitting. While the phenomenon is established in organic chiral molecules, its emergence in chiral but inorganic, nonmolecular materials is not yet understood. Nevertheless, inorganic spin-filtering materials offer favorable characteristics, such as thermal and chemical stability, over organic, molecular spin filters. Chiral cupric oxide (CuO) thin films can spin polarize (photo)electron currents, and this capability is linked to the occurrence of the CISS effect. In the present work, chiral CuO films, electrochemically deposited on partially UV-transparent polycrystalline gold substrates, were subjected to deep-UV laser pulses, and the average spin polarization of photoelectrons was measured in a Mott scattering apparatus. By energy resolving the photoelectrons and changing the photoexcitation geometry, the energy distribution and spin polarization of the photoelectrons originating from the Au substrate could be distinguished from those arising from the CuO film. The findings reveal that the spin polarization is energy dependent and, furthermore, indicate that the measured polarization values can be rationalized as a sum of an intrinsic spin polarization in the chiral oxide layer and a contribution via CISS-related spin filtering of electrons from the Au substrate. The results support efforts toward a rational design of further spin-selective catalytic oxide materials.

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin-orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect.

Chirality in life has been preserved throughout evolution. It has been assumed that the main function of chirality is its contribution to structural properties. In the past two decades, however, it has been established that chiral molecules possess unique electronic properties. Electrons that pass through chiral molecules, or even charge displacements within a chiral molecule, do so in a manner that depends on the electron's spin and the molecule's enantiomeric form. This effect, referred to as chiral induced spin selectivity (CISS), has several important implications for the properties of biosystems. Among these implications, CISS facilitates long-range electron transfer, enhances bio-affinities and enantioselectivity, and enables efficient and selective multi-electron redox processes. In this article, we review the CISS effect and some of its manifestations in biological systems. We argue that chirality is preserved so persistently in biology not only because of its structural effect, but also because of its important function in spin polarizing electrons.

We investigate a spin-boson inspired model of electron transfer, where the diabatic coupling is given by a position-dependent phase, e iWx . We consider both equilibrium and nonequilibrium initial conditions. We show that, for this model, all equilibrium results are completely invariant to the sign of W (to infinite order). However, the nonequilibrium results do depend on the sign of W, suggesting that photo-induced electron transfer dynamics with spin-orbit coupling can exhibit electronic spin polarization (at least for some time).

There is increasing interest in the study of chiral degrees of freedom occurring in matter and in electromagnetic fields. Opportunities in quantum sciences will likely exploit two main areas that are the focus of this Review: (1) recent observations of the chiral-induced spin selectivity (CISS) effect in chiral molecules and engineered nanomaterials and (2) rapidly evolving nanophotonic strategies designed to amplify chiral light-matter interactions. On the one hand, the CISS effect underpins the observation that charge transport through nanoscopic chiral structures favors a particular electronic spin orientation, resulting in large room-temperature spin polarizations. Observations of the CISS effect suggest opportunities for spin control and for the design and fabrication of room-temperature quantum devices from the bottom up, with atomic-scale precision and molecular modularity. On the other hand, chiral-optical effects that depend on both spin- and orbital-angular momentum of photons could offer key advantages in all-optical and quantum information technologies. In particular, amplification of these chiral light-matter interactions using rationally designed plasmonic and dielectric nanomaterials provide approaches to manipulate light intensity, polarization, and phase in confined nanoscale geometries. Any technology that relies on optimal charge transport, or optical control and readout, including quantum devices for logic, sensing, and storage, may benefit from chiral quantum properties. These properties can be theoretically and experimentally investigated from a quantum information perspective, which has not yet been fully developed. There are uncharted implications for the quantum sciences once chiral couplings can be engineered to control the storage, transduction, and manipulation of quantum information. This forward-looking Review provides a survey of the experimental and theoretical fundamentals of chiral-influenced quantum effects and presents a vision for their possible future roles in enabling room-temperature quantum technologies.

This study presents a halide exchange mediated cation exchange strategy for a room temperature doping of trivalent lanthanide cations (Ln 3+ ) in cesium lead halide (CsPbX 3 ) nanoparticles (NPs). Post-synthetic addition of LnCl 3 [Ln = Nd, Sm, Eu, Tb, Dy, and Yb] to a solution of CsPbBr 3 NPs generates the corresponding lanthanide doped NPs which display host sensitized Ln 3+ emission. Structural and spectroscopic characterizations indicate a successful halide exchange and substitutional displacement of Pb 2+ by Ln 3+ . The effect of halide identity in controlling the Ln 3+ sensitization was also evaluated. A photophysical framework is presented that can be used to predict the Ln 3+ sensitization in perovskite NPs semiempirically, thereby removing the constraints of trial and error in designing a perovskite NP-Ln 3+ host-guest combination.

A critical overview of the theory of the chirality-induced spin selectivity (CISS) effect, that is, phenomena in which the chirality of molecular species imparts significant spin selectivity to various electron processes, is provided. Based on discussions in a recently held workshop, and further work published since, the status of CISS effects-in electron transmission, electron transport, and chemical reactions-is reviewed. For each, a detailed discussion of the state-of-the-art in theoretical understanding is provided and remaining challenges and research opportunities are identified., (© 2022 Wiley-VCH GmbH.)

This study presents a post-synthetic ligand modification strategy for the generation of chiroptically active, blue emitting CsPbBr 3 nanoparticles (NPs) - an expansion to the library of 3D chiral perovskite nanomaterials. Addition of [ R - and S -] 1-phenylethylamine, 1-(1-naphthyl)ethylamine, or 2-aminooctane to the synthesized CsPbBr 3 NPs is shown to induce Cotton effects in the NP first exciton transition, suggestive of a successful electronic coupling between the chiral ligands and the NPs. The availability of these chiral CsPbBr 3 NPs thrusts them into the forefront of perovskite nanomaterials for examining the implications of the chiral induced spin selectivity (CISS) effect and other applications in spintronics.

This work uses electrochemical quartz crystal microbalance methods to demonstrate the enantiospecific interaction between a magnetized surface and a chiral amino acid. The enantiospecific adsorption of chiral molecules (cysteine is used as a model) on a ferromagnetic surface is shown to arise from the kinetics of adsorption and not from a thermodynamic stabilization. Measurements of the Gibbs free energy of adsorption for different chiral forms of cysteine and different electrode magnetization states show no significant differences, whereas measurements of the adsorption and desorption kinetics reveal a strong dependence on the magnetization state of the electrode surface. In addition, the enantioselectivity is shown to depend sensitively on the solution pH and the charge state of the chiral adsorbate.

The detection of enantiopurity for small sample quantities is crucial, particularly in the pharmaceutical industry; however, existing methodologies rely on specific chiral recognition elements, or complex optical systems, limiting its utility. A nanoscale chirality sensor, for continuously monitoring molecular chirality using an electric circuit readout, is presented. This device design represents an alternative real-time scalable approach for chiral recognition of small quantity samples (less than 10 3 adsorbed molecules). The active device component relies on a gold nanofloret hybrid structure, i.e., a high aspect ratio semiconductor-metal hybrid nanosystem in which a SiGe nanowire tip is selectively decorated with a gold metallic cap. The tip mechanically touches a counter electrode to generate a nanojunction, and upon exposure to molecules, a metal-molecule-metal junction is formed. Adsorption of chiral molecules at the gold tip induces chirality in the localized plasmonic resonance at the electrode-tip junction and manifests in an enantiospecific current response.

The steady-state charge and spin transfer yields were measured for three different Ru-modified azurin derivatives in protein films on silver electrodes. While the charge-transfer yields exhibit weak temperature dependences, consistent with operation of a near activation-less mechanism, the spin selectivity of the electron transfer improves as temperature increases. This enhancement of spin selectivity with temperature is explained by a vibrationally induced spin exchange interaction between the Cu(II) and its chiral ligands. These results indicate that distinct mechanisms control charge and spin transfer within proteins. As with electron charge transfer, proteins deliver polarized electron spins with a yield that depends on the protein's structure. This finding suggests a new role for protein structure in biochemical redox processes., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The flow of charge through molecules is central to the function of supramolecular machines, and charge transport in nucleic acids is implicated in molecular signaling and DNA repair. We examine the transport of electrons through nucleic acids to understand the interplay of resonant and nonresonant charge carrier transport mechanisms. This study reports STM break junction measurements of peptide nucleic acids (PNAs) with a G-block structure and contrasts the findings with previous results for DNA duplexes. The conductance of G-block PNA duplexes is much higher than that of the corresponding DNA duplexes of the same sequence; however, they do not display the strong even-odd dependence conductance oscillations found in G-block DNA. Theoretical analysis finds that the conductance oscillation magnitude in PNA is suppressed because of the increased level of electronic coupling interaction between G-blocks in PNA and the stronger PNA-electrode interaction compared to that in DNA duplexes. The strong interactions in the G-block PNA duplexes produce molecular conductances as high as 3% G 0 , where G 0 is the quantum of conductance, for 5 nm duplexes.

High entropy alloy nanoparticles (HEA-NPs) are expanding their influence in many fields. To explore the electronic structures in such multielemental systems, HEA-NPs were synthesized on two different carbon substrates through carbothermal shock and in situ reduction methods. The relationship between the apparent core level energy shifts (negative or positive) and the electron density changes among the components of quinary-metal HEA-NPs was investigated by X-ray photoelectron spectroscopy (XPS) analysis and first-principles electronic structure calculations. It was found that Cu displays a negative core level shift while Fe, Co, Mg, Cr, and Mn display a positive core level shift. While experiments show an apparent positive core level shift for Ni, electronic structure calculations reveal that this arises from shifts in the Fermi level and that the electron density redistribution in Ni behaves more like Cu than the other elements. The findings show that the electron density redistribution in the NPs occurs from less electronegative elements to more electronegative ones. This work should guide the design of HEA-NPs to expand their potential applications in mechanical structures, medicine, catalysis, and energy storage/conversion.

The technological advancement of data storage is reliant upon the continuous development of faster and denser memory with low power consumption. Recent progress in flash memory has focused on increasing the number of bits per cell to increase information density. In this work an optical multilevel spin bit, based on the chiral induced spin selectivity (CISS) effect, is developed using nanometer sized chiral quantum dots. A double quantum dot architecture is adsorbed on the active area of a Ni based Hall sensor and a nine-state readout is achieved.

The electron's spin, its intrinsic angular momentum, is a quantum property that plays a critical role in determining the electronic structure of molecules. Despite its importance, it is not used often for controlling chemical processes, photochemistry excluded. The reason is that many organic molecules have a total spin zero, namely, all the electrons are paired. Even for molecules with high spin multiplicity, the spin orientation is usually only weakly coupled to the molecular frame of nuclei and hence to the molecular orientation. Therefore, controlling the spin orientation usually does not provide a handle on controlling the geometry of the molecular species during a reaction. About two decades ago, however, a new phenomenon was discovered that relates the electron's spin to the handedness of chiral molecules and is now known as the chiral induced spin selectivity (CISS) effect. It was established that the efficiency of electron transport through chiral molecules depends on the electron spin and that it changes with the enantiomeric form of a molecule and the direction of the electron's linear momentum. This property means that, for chiral molecules, the electron spin is strongly coupled to the molecular frame. Over the past few years, we and others have shown that this feature can be used to provide spin-control over chemical reactions and to perform enantioseparations with magnetic surfaces.In this Account, we describe the CISS effect and demonstrate spin polarization effects on chemical reactions. Explicitly, we describe a number of processes that can be controlled by the electron's spin, among them the interaction of chiral molecules with ferromagnetic surfaces, the multielectron oxidation of water, and enantiospecific electrochemistry. Interestingly, it has been shown that the effect also takes place in inorganic chiral oxides like copper oxide, aluminum oxide, and cobalt oxide. The CISS effect results from the coupling between the electron linear momentum and its spin in a chiral system. Understanding the implications of this interaction promises to reveal a previously unappreciated role for chirality in biology, where chiral molecules are ubiquitous, and opens a new avenue into spin-controlled processes in chemistry.

Essential aspects of the chiral induced spin selectivity (CISS) effect and their implications for spin-controlled chemistry and asymmetric electrochemical reactions are described. The generation of oxygen through electrolysis is discussed as an example in which chirality-based spin-filtering and spin selection rules can be used to improve the reaction's efficiency and selectivity. Next the discussion shifts to illustrate how the spin selectivity of chiral molecules (CISS properties) allows one to use the electron spin as a chiral bias for inducing asymmetric reactions and promoting enantiospecific processes. Two enantioselective electrochemical reactions that have used polarized electron spins as a chiral reagent are described; enantioselective electroreduction to resolve an enantiomer from a racemic mixture and an oxidative electropolymerization to generate a chiral polymer from achiral monomers. A complementary approach that has used spin-polarized, but otherwise achiral, molecular films to enantiospecifically associate with one enantiomer from a racemic mixture is also discussed. Each of these reaction types use magnetized films to generate the spin polarized electrons and the enantiospecificity can be selected by choice of the magnetization direction, North pole versus South pole. Possible paths for future research in this area and its compatibility with existing methods based on chiral electrodes are discussed.

We report the hydrothermally enhanced hydrolysis of polyacrylonitrile (PAN) in neutral water, which generates photoluminescent polymers with low unsaturation degrees. Despite the hydrophobic nature of PAN, the product can be dissolved in water at a high concentration (≥100 g/L). The product exhibits complete absence of alkenes or aromatic structures, and photoluminescence originates from newly formed N- and O-containing groups. The presence of both n to π* and π to π* transitions is confirmed by time-dependent density functional theory (TD-DFT) calculations. The efficient transformation of PAN benefits from the enhanced hydrolysis of nitrile groups. While similar reactions have been reported previously under alkaline environments, we demonstrate that efficient hydrolysis can also occur in neutral water under the hydrothermal condition. Two additional methods based on different mechanisms are discussed to demonstrate the simplicity and efficiency of the hydrothermal reaction.

The recent convergence of chiral molecules with metal halide perovskite frameworks gives rise to an interesting family of chiral systems: two-dimensional, chiral hybrid organic-inorganic perovskites (chiral-HOIPs). While possessing photovoltaic properties of traditional HOIPs, this class of materials is endowed with chirality through its organic ligands in which the degeneracy of the electron spin in charge transport is broken. That is, the chirality-induced spin selectivity (CISS) effect manifests, making it a promising platform to bridge opto-spintronic studies and the CISS effect. In this work, chiral-HOIP/NiFe heterostructures are studied by means of the magneto-optical Kerr effect using a Sagnac interferometer. Upon illumination of the chiral-HOIPs, the Kerr signal at the chiral-HOIP/NiFe interface changes, and a linear dependence of the response on the magnetic field is observed. The sign of the slope was found to depend on the chirality of the HOIPs. The results demonstrate the utility of chiral-HOIP materials for chiral opto-spintronic applications.

This Perspective discusses recent experiments that bear on the chiral induced spin selectivity (CISS) mechanism and its manifestation in electronic and magnetic properties of chiral molecules and materials. Although the discussion emphasizes newer experiments, such as the magnetization dependence of chiral molecule interactions with ferromagnetic surfaces, early experiments, which reveal the nonlinear scaling of the spin filtering with applied potential, are described also. In many of the theoretical studies, one has had to invoke unusually large spin-orbit couplings in order to reproduce the large spin filtering observed in experiments. Experiments imply that exchange interactions and Pauli exclusion constraints are an important aspect of CISS. They also demonstrate the spin-dependent charge flow between a ferromagnetic substrate and chiral molecules. With these insights in mind, a simplified model is described in which the chiral molecule's spin polarization is enhanced by a spin blockade effect to generate large spin filtering.

Kelvin-probe measurements on ferromagnetic thin film electrodes coated with self-assembled monolayers of chiral molecules reveal that the electron penetration from the metal electrode into the chiral molecules depends on the ferromagnet's magnetization direction and the molecules' chirality. Electrostatic potential differences as large as 100 mV are observed. These changes arise from the applied oscillating electric field, which drives spin-dependent charge penetration from the ferromagnetic substrate to the chiral molecules. The enantiospecificity of the response is studied as a function of the magnetization strength, the magnetization direction, and the handedness and length of the chiral molecules. These new phenomena are rationalized in terms of the chiral-induced spin selectivity (CISS) effect, in which one spin orientation of electrons from the ferromagnet penetrates more easily into a chiral molecule than does the other orientation. The large potential changes (>kT at room temperature) manifested here imply that this phenomenon is important for spin transport in chiral spintronic devices and for magneto-electrochemistry of chiral molecules.

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin-polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron-spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self-assembled monolayer film that is spin-polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron-spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Optical control and readout of electron spin and spin currents in thin films and nanostructures have remained attractive yet challenging goals for emerging technologies designed for applications in information processing and storage. Recent advances in room-temperature spin polarization using nanometric chiral molecular assemblies suggest that chemically modified surfaces or interfaces can be used for optical spin conversion by exploiting photoinduced charge separation and injection from well-coupled organic chromophores or quantum dots. Using light to drive photoexcited charge-transfer processes mediated by molecules with central or helical chirality enables indirect measurements of spin polarization attributed to the chiral-induced spin selectivity effect and of the efficiency of spin-dependent electron transfer relative to competitive relaxation pathways. Herein, we highlight recent approaches used to detect and to analyze spin selectivity in photoinduced charge transfer including spin-transfer torque for local magnetization, nanoscale charge separation and polarization, and soft ferromagnetic substrate magnetization- and chirality-dependent photoluminescence. Building on these methods through systematic investigation of molecular and environmental parameters that influence spin filtering should elucidate means to manipulate electron spins and photoexcited states for room-temperature optoelectronic and photospintronic applications.