Electron Affinity Research Articles

Low-energy electron driven reactions in 2-bromo-5-nitrothiazole.

Thiazole derivatives are biologically relevant molecules, used also in pharmaceutical applications. Herein, we report results for electron attachment to 2-bromo-5-nitrothiazole (BNT) in the gas phase. Employing two crossed electron-molecule beam experiments, we determined the efficiency curves of various fragment anions as a function of the initial electron energy between about 0 and 10eV as well as the emission angle and kinetic energy distributions of Br- and NO2- ions formed from a resonance near 4eV. The experiments were supported by quantum chemical calculations, exploring possible dissociation pathways along with their reaction energies. We also compared the electron attachment characteristics of BNT with those of the native thiazole molecule by performing electron attachment experiments and calculations for this molecule as well. Compared to thiazole, which is primarily degraded only by electrons with kinetic energies between about 5 and 10eV, BNT is susceptible to low-energy electrons near 0eV with enhanced cross section for (dissociative) electron attachment. However, although BNT offers two localization sites with high electron affinity (Br and NO2 moieties), we do not find the corresponding anions as the dominant negatively charged species formed upon electron attachment. Instead, the reaction channels with an abstraction of Br and NO2 as neutral radicals prevail, accompanied by the opening of the thiazole ring due to the relatively weak C-S bond.

Theoretical insights of ionization potential and electron affinity modulations on planar vs. ruffled iron(III) porphyrins

Theoretical insights of ionization potential and electron affinity modulations on planar vs. ruffled iron(III) porphyrins

Synthesis of Pyrene Diimide Isomers with Tunable Excimer Emission.

The optoelectronic properties of pyrene diimides (PyDIs) are of strategic interest given the successful application of similar rylene diimides as n-type organic semiconductors in a variety of organic electronics. We present an improved synthesis for 1,5,6,10-pyrene diimide and the first report of its isomer, 1,8,9,10-pyrene diimide. We demonstrate the effect of imide placement on the core structure, optical properties, and electron affinities. Notably, we have discovered that both isomers exhibit tunable aggregation-induced excimer emission and that 1,8,9,10-PyDI exhibits anti-Kasha emission.

Quantum chemical study of molecular properties of small branched-chain amino acids in water

Four aliphatic amino acids—α-aminobutyric acid (AABA), β-aminobutyric acid (BABA), α-aminoisobutyric acid (AAIBA) and β-aminoisobutyric acid (BAIBA) were investigated in water as a solvent by two quantum chemical methods. B3LYP hybrid version of DFT was used for geometry optimization and a full vibrational analysis of neutral molecules, their cations and anions in the canonical and zwitterionic forms (6 forms for each species). Ab initio DLPNO-CCSD(T) method was applied in the geometry pre-optimized by B3LYP. Calculated molecular descriptors involve dipole moment, quadrupole moment, dipole polarizability, energy of zero-point vibration and total entropic term which enter the standard Gibbs energy. In addition, a set of collective electronic and thermodynamic properties associated with redox process were evaluated: ionization energy, electron affinity, chemical hardness, molecular electronegativity, electrophilicity index, absolute oxidation and reduction potentials. A mutual comparison of these structural isomers including γ-aminobutyric acid (GABA) shows high degree of similarity in molecular descriptors. However, cluster analysis of 12 electro neutral, linear and branched amino acids with 2 – 6 carbon atoms discriminates them into five clusters. It is found that the electrophilicity index correlates with the absolute reduction potential along a straight line (24 items). The reduction potential for canonical structure varies between 1.21 V (glycine) and 1.45 V (AABA) whereas for the zwitterionic form it is visibly lower 0.52–1.11 V. The highest absolute reduction potential > 1.43 V is shown by α-amino acids: α-alanine, AABA (homoalanine) and AAIBA having 2-methyl or 2-ethyl functional group. The calculated absolute oxidation potential correlates with the adiabatic ionization energy and can be used as a criterion of the antioxidant capacity. According to thermodynamic data, the SPLET mechanism of the electron-proton coupled transfer is favored over the alternative SET-PT mechanism. This work contributes to the creation of a database of molecular properties of amino acids based on the same method and basis set.

Compressing slippery surface-assembled amphiphiles for tunable haptic energy harvesters.

A recurring challenge in extracting energy from ambient motion is that devices must maintain high harvesting efficiency and a positive user experience when the interface is undergoing dynamic compression. We show that small amphiphiles can be used to tune friction, haptics, and triboelectric properties by assembling into specific conformations on the surfaces of materials. Molecules that form multiple slip planes under pressure, especially through π-π stacking, produce 80 to 90% lower friction than those that form disordered mesostructures. We propose a scaling framework for their friction reduction properties that accounts for adhesion and contact mechanics. Amphiphile-coated surfaces tend to resist wear and generate distinct tactile perception, with humans preferring more slippery materials. Separately, triboelectric output is enhanced through the use of amphiphiles with high electron affinity. Because device adoption is tied to both friction reduction and electron-withdrawing potential, molecules that self-organize into slippery planes under pressure represent a facile way to advance the development of haptic power harvesters at scale.

Photoelectron Imaging and Photodetachment Spectroscopy for the Cryogenically Cooled Cyanocyclopentadienide Anion.

The cyano-cyclopentadiene molecule (CN-C5H5) has attracted significant interest since its detection in the interstellar medium, but the radical (CN-C5H4) and anionic (CN-C5H4-) forms of cyano-cyclopentadiene have not been studied. The cyano-cyclopentadienyl radical (CN-Cp) has a strong dipole moment, rendering it an ideal system for vibrational and rotational spectroscopy. We report an investigation of the cryogenically cooled cyano-cyclopentadienide anion (CN-Cp-) using high-resolution photoelectron imaging, photodetachment spectroscopy, and resonant photoelectron imaging. The electron affinity of the CN-Cp radical is measured accurately to be 2.7741 ± 0.0003 eV (22,375 ± 2 cm-1). A low-lying excited state is observed for the CN-Cp neutral radical at 151 cm-1 above the ground state. The overlap and vibronic coupling of the ground and low-lying electronic states give rise to complicated and congested photoelectron spectra. A dipole-bound state is observed for the CN-Cp- anion with a binding energy of 94 cm-1, along with 15 vibrational Feshbach resonances. Resonant photoelectron spectra via the vibrational resonances yield well-resolved spectra, allowing 26 vibronic levels to be identified for CN-Cp. The rich spectroscopic information will be valuable to compare with theoretical studies to unravel the vibronic coupling and nonadiabatic effects in the CN-Cp radical.

Integer Charge Transfer Model-PTCDA on MgO(001)/Ag(001) Probing the Transition from Single to Double Integer Charge Transfer.

For weakly interacting adsorbate/substrate systems, the integer charge transfer (ICT) model describes how charge transfer across interfaces depends on the substrate work function. In particular, work function regimes where no charge transfer occurs (vacuum level alignment) can be distinguished from regions where integer charge transfer by electron tunneling from substrate to adsorbate or vice versa takes place (Fermi level pinning). While the formation of singly integer charged molecular anions and cations of organic semiconductors on various substrates has been well described by this model, the double integer charging regime has so far remained unexplored and experimentally elusive. Here, we extend the integer charge transfer model to the transition from single to double integer charging. This was made possible by combining a molecular adsorbate with high electron affinity (Perylenetetracarboxylic-dianhydride (PTCDA)) with a substrate with tunable work function (ultrathin MgO(001) films on Ag(001)). Our results, obtained with scanning tunneling microscopy (STM), photoemission spectroscopy (PES), work function measurements and density function theory (DFT) calculations, show that after completing the single negative charging of all molecules in a PTCDA monolayer in the first Fermi level pinning regime, the system transitions to a vacuum level alignment regime for singly charged molecules when the substrate work function is reduced, and finally enters the second Fermi level pinning regime at very low substrate work function, in which the molecules become doubly negatively charged.

Dynamically Stable Cu0Cuδ+ Pair Sites Based on In Situ‐Exsolved Cu Nanoclusters on CaCO3 for Efficient CO2 Electroreduction

AbstractCopper‐based catalysts are the choice for producing multi‐carbon products (C2+) during CO2 electroreduction (CO2RR), where the Cu0Cuδ+ pair sites are proposed to be synergistic hotspots for C−C coupling. Maintaining their dynamic stability requires precise control over electron affinity and anion vacancy formation energy, posing significant challenges. Here, we present an in situ reconstruction strategy to create dynamically stable Cu0Cu0.18+OCa motifs at the interface of exsolved Cu nanoclusters and CaCO3 nanospheres (Cu/CaCO3). In situ XAFS analysis confirmed the low‐valency state of Cuδ+ during CO2RR. DFT calculations demonstrated that the nanocluster size arises from the balance between metal‐support interactions and Cu−Cu cohesive energy, while the dynamic stability of rich interfacial Cuδ+ sites is attributed to their low electron affinity and high CO32− vacancy formation energy, which collectively contribute to reduced reducibility. The transformed Cu/CaCO3 exhibits an impressive C2+ Faradaic efficiency of 83.7 % at a partial current density of 393 mA cm−2, facilitated by adsorption of *CO with varying electronegativity at heterogeneous copper sites that lowers the C−C coupling energy barrier. Our findings establish insoluble carbonate as an effective anion pairing for Cu0Cuδ+ sites, highlighting the effectiveness of the in situ reconstitution strategy in producing a high density of dynamically stable Cu0Cuδ+ pair sites.

Tetrahedral Al20O30 Cage: A Superchalcogen Atom.

Superatoms are stable clusters that mimic the chemical behavior of individual atoms in the periodic table. Many endeavors have been devoted to the design and characterization of various superatoms, while engineering superatoms to mimic the chemistry of chalcogens remains a challenge. In this paper, we present a new superchalcogen by evaluating a hollow tetrahedral Al20O30 cluster with theoretical calculations. By comparing the Al20O30 with its daughter dianion (Al20O30)2- in terms of stability, aromaticity, electronic properties, and chemical behavior in compounds, we find that this cluster tends to get two additional electrons to reach a more stable electronic state, which is the origin of the identity of superchalcogens. The adaptive natural density partitioning (AdNDP) analysis illustrates that this Al20O30 cluster accommodates two electrons by a 4-center-2-electron bond formed between the four face-centered Al atoms. Moreover, the Al20O30 cluster has exothermic first and second adiabatic electron affinity (EA), indicating that the dianion (Al20O30)2- is stable against spontaneous electron emission and fragmentation in the gas phase. This reflects the size advantage of superchalcogens when compared with chalcogens. Interestingly, we further study a cluster with one more electron than the superchalcogen Al20O30, namely, H@(Al20O30) and find that it is a superhalogen due to its large vertical and adiabatic EA.

Cs- O2 -Li as enhanced NEA surface layer with increased lifetime for GaAs photocathodes

GaAs-based photocathodes are the only viable source capable of providing spin-polarized electrons for accelerator applications. This type of photocathode requires a thin surface layer, in order to achieve negative electron affinity (NEA) for efficient photoemission. However, this layer is vulnerable to environmental and operational effects, leading to a decay of the quantum efficiency η characterized by a decay constant or lifetime τ. In order to increase τ, additional agents can be introduced during the activation procedure to improve the chemical robustness of the surface layer. This paper presents the results of recent research on Li as an enhancement agent for photocathode activation using Cs and O2, forming Cs-O2-Li as an enhanced NEA layer. Measurements yielded an increase in lifetime by a factor of up to 19±2 and an increase in extracted charge by a factor of up to 16.5±2.4, without significant reduction of η. This performance is equal to or better than that reported for other enhanced NEA layers so far. Published by the American Physical Society 2025

Tuning electronic structure and carrier transport properties through crystal orientation control in two-dimensional Dion-Jacobson phase perovskites

Two-dimensional halide perovskites are attracting attention due to their structural diversity, improved stability, and enhanced quantum efficiency compared to their three-dimensional counterparts. In particular, Dion-Jacobson (DJ) phase perovskites exhibit superior structural stability compared to Ruddlesden-Popper phase perovskites. The inherent quantum well structure of layered perovskites leads to highly anisotropic charge transport and optical properties. Therefore, controlling the preferred crystal orientation (parallel or perpendicular) is crucial for optimizing device performance. This work presents a rational strategy to control parallel and perpendicular crystal growth in C6N2H16PbI4 (4AMPPbI4)-based DJ phase perovskite thin films. We demonstrate that crystal orientation depends on crystal growth rates, which can be controlled by varying the solvent composition, antisolvent, and annealing temperature. Direct and inverse photoelectron spectroscopy reveals that the electronic structure of 4AMPPbI4, including its work function, ionization energy, and electron affinity, is orientation-dependent. Different orientations significantly affect carrier transport as confirmed by single-carrier devices. This study highlights the critical role of crystal orientation in DJ phase perovskites for designing high-performance optoelectronic devices.Graphical

Molecular Order Induced Charge Transfer in a C60-Topological Insulator Moiré Heterostructure.

We synthesized and spectroscopically investigated monolayer (ML) C60 on the topological insulator (TI) Bi4Te3. This C60/Bi4Te3 heterostructure is characterized by an excellent translational order in a novel (4 × 4) C60 superstructure on a (9 × 9) cell of Bi4Te3. Angle-resolved photoemission spectroscopy (ARPES) of C60/Bi4Te3 reveals that ML C60 accepts electrons from the TI at room temperature, but no charge transfer occurs at low temperatures. This temperature-dependent doping is further investigated by Raman spectroscopy, photoluminescence (PL), and calculations of C60/Bi4Te3. At low temperatures, Raman spectroscopy and PL show a dramatic intensity increase of the C60-related signal, suggesting a transition to a rotationally ordered state. Calculations explain the charge transfer by C60 adsorption to Bi4Te3 surface defects. The temperature dependence of the charge transfer is attributed to the orientational order of C60. The electron affinity of C60 increases at low temperatures due to the freezing of the rotational motion.

Dynamically Stable Cu0Cuδ+ Pair Sites Based on In Situ-Exsolved Cu Nanoclusters on CaCO3 for Efficient CO2 Electroreduction.

Copper-based catalysts are the choice for producing multi-carbon products (C2+) during CO2 electroreduction (CO2RR), where the Cu0Cuδ+ pair sites are proposed to be synergistic hotspots for C-C coupling. Maintaining their dynamic stability requires precise control over electron affinity and anion vacancy formation energy, posing significant challenges. Here, we present an in situ reconstruction strategy to create dynamically stable Cu0Cu0.18+OCa motifs at the interface of exsolved Cu nanoclusters and CaCO3 nanospheres (Cu/CaCO3). In situ XAFS analysis confirmed the low-valency state of Cuδ+ during CO2RR. DFT calculations demonstrated that the nanocluster size arises from the balance between metal-support interactions and Cu-Cu cohesive energy, while the dynamic stability of rich interfacial Cuδ+ sites is attributed to their low electron affinity and high CO3 2- vacancy formation energy, which collectively contribute to reduced reducibility. The transformed Cu/CaCO3 exhibits an impressive C2+ Faradaic efficiency of 83.7 % at a partial current density of 393 mA cm-2, facilitated by adsorption of *CO with varying electronegativity at heterogeneous copper sites that lowers the C-C coupling energy barrier. Our findings establish insoluble carbonate as an effective anion pairing for Cu0Cuδ+ sites, highlighting the effectiveness of the in situ reconstitution strategy in producing a high density of dynamically stable Cu0Cuδ+ pair sites.

Inverse design of copolymers including stoichiometry and chain architecture.

The demand for innovative synthetic polymers with improved properties is high, but their structural complexity and vast design space hinder rapid discovery. Machine learning-guided molecular design is a promising approach to accelerate polymer discovery. However, the scarcity of labeled polymer data and the complex hierarchical structure of synthetic polymers make generative design particularly challenging. We advance the current state-of-the-art approaches to generate not only repeating units, but monomer ensembles including their stoichiometry and chain architecture. We build upon a recent polymer representation that includes stoichiometries and chain architectures of monomer ensembles and develop a novel variational autoencoder (VAE) architecture encoding a graph and decoding a string. Using a semi-supervised setup, we enable the handling of partly labelled datasets which can be beneficial for domains with a small corpus of labelled data. Our model learns a continuous, well organized latent space (LS) that enables de novo generation of copolymer structures including different monomer stoichiometries and chain architectures. In an inverse design case study, we demonstrate our model for in silico discovery of novel conjugated copolymer photocatalysts for hydrogen production using optimization of the polymer's electron affinity and ionization potential in the latent space.

Enhancing the tribopositive characteristics of polyvinyl alcohol (PVA)-carbon composites by optimizing the PVA-carbon interaction with various carbon fillers.

Incorporating carbon-based fillers into triboelectric nanogenerators, TENGs, is a compelling strategy to enhance the power output. However, the lack of systematic studies comparing various carbon fillers and their impact on tribopositive contact layers necessitates further research. To address these concerns, various carbon fillers (including buckminsterfullerene (C60), graphene oxide (GO), reduced graphene oxide (rGO), multi-wall carbon nanotube (MWCNT), and super activated carbon (SAC)) with distinct structural and electrical properties are mixed with polyvinyl alcohol, PVA, to form PVA-carbon composites and used as tribopositive layers in the contact-separation of TENGs. The results show that PVA-SAC provides the largest enhancements to the electrical outputs of the TENG. At the optimal loading of 1 wt%, PVA-SAC composites yielded a peak power density of 12.8 W m-2, a substantial 220% enhancement compared to pristine PVA. The mechanism governing the enhancement is determined by analysing the changes in electrical and structural characteristics caused by the addition of various carbon fillers. Dielectric measurements indicated that enhanced dielectric properties did not significantly contribute to the observed increase in the triboelectric performance. Instead, Raman and FTIR analyses revealed a correlation between the PVA-carbon interactions and an increase in the D/G ratio of carbon fillers, accompanied by a reduction in hydrogen-bonded -OH groups within PVA. This suggests that the interaction between the π electrons of sp2 hybridized carbon atoms and the oxygen lone pairs in PVA inhibits hydrogen bond formation, leading to an increase in free -OH groups. Consequently, these free -OH groups enhanced the electron-donating capability and improved the tribopositive behaviour of the PVA-carbon composites. Our results proved that filler-matrix interactions are paramount in engineering high-performance TENGs by controlling the electron affinity of the triboelectric layers.

Direct ink writing of nickel oxide-based thin films for room temperature gas detection

The rapid industrial growth and increasing population have led to significant pollution and deterioration of the natural atmospheric environment. Major atmospheric pollutants include NO2 and CO2. Hence, it is imperative to develop NO2 and CO2 sensors for ambient conditions, that can be used in indoor air quality monitoring, breath analysis, food spoilage detection, etc. In the present study, two thin film nanocomposite (nickel oxide-graphene and nickel oxide-silver nanowires) gas sensors are fabricated using direct ink writing. The nano-composites are investigated for their structural, optical, and electrical properties. Later the nano-composite is deposited on the interdigitated electrode (IDE) pattern to form NO2 and CO2 sensors. The deposited films are then exposed to NO2 and CO2 gases separately and their response and recovery times are determined using a custom-built gas sensing setup. Nickel oxide-graphene provides a good response time and recovery time of 10 and 9 s, respectively for NO2, due to the higher electron affinity of graphene towards NO2. Nickel oxide-silver nanowire nano-composite is suited for CO2 gas because silver is an excellent electrocatalyst for CO2 by giving response and recovery times of 11 s each. This is the first report showcasing NiO nano-composites for NO2 and CO2 sensing at room temperature.

Electrochemical reduction for chlorinated hydrocarbons contaminated groundwater remediation: Mechanisms, challenges, and perspectives.

Electrochemical reduction technology is a promising method for addressing the persistent contamination of groundwater by chlorinated hydrocarbons. Current research shows that electrochemical reductive dechlorination primarily relies on direct electron transfer (DET) and active hydrogen (H⁎) mediated indirect electron transfer processes, thereby achieving efficient dechlorination and detoxification. This paper explores the influence of the molecular charge structure of chlorinated hydrocarbons, including chlorolefin, chloroalkanes, chlorinated aromatic hydrocarbons, and chloro-carboxylic acid, on reductive dechlorination from the perspective of molecular electrostatic potential and local electron affinity. It reveals the affinity characteristics of chlorinated hydrocarbon pollutants, the active dechlorination sites, and the roles of substituent groups. It also comprehensively discusses the current progress on electrochemical reductive dechlorination using metal, carbon-based, and 3D electrode catalysts, with an emphasis on the design and optimization of electrode materials and the impact of catalyst microstructure regulation on dechlorination performance. It delves into the current application status of coupling electrochemical reduction technology with biodegradation and electrochemical circulating well technology for the remediation of groundwater contaminated by chlorinated hydrocarbons. The paper discusses practical application challenges such as electron transfer, electrode corrosion, water chemistry environment, and aquifer heterogeneity. Finally, considerations are presented from the perspectives of environmental impact and sustainable application, along with a summary and analysis of potential future research directions and technological prospects.

Single atom alloys aggregation in the presence of ligands.

Single atom alloys (SAAs) have gained tremendous attention as promising materials with unique physicochemical properties, particularly in catalysis. The stability of SAAs relies on the formation of a single active dopant on the surface of a metal host, quantified by the surface segregation and aggregation energy. Previous studies have investigated the surface segregation of non-ligated and ligated SAAs to reveal the driving forces underlying such phenomena. In this work we address another key factor dictating the stability in non-ligated and ligated SAAs: the aggregation energy (Eagg) of dopants. Specifically, we examine how thiols and amines, commonly found ligands in colloidal bimetallic nanoparticle synthesis, affect the aggregation of dopants (forming dimers and trimers) on the surface of a metal host. Utilizing Density Functional Theory (DFT) and machine learning (ML), we explore the stability patterns of SAAs through the energetics of low-index surfaces, such as (111) and (100), consisting of d8-(Pt, Pd, Ni) and d9-(Ag, Au, Cu) metals, both in the presence and absence of ligands. Collecting rich and accurate DFT data, we developed a four-feature support vector regression using the radial basis function (SVR RBF) to predict the Eagg. The model revealed important and easily accessible (tabulated) thermodynamic stability features that drive metal aggregation in SAAs, such as the bulk cohesive energy of the metal considering the exposed coordination environment on the surface, the charge transfer represented by the difference in electron affinities of metals and the radii of the metals describing strain effects. Additional incorporated features include adsorbate properties, such as the binding energy of the ligand on a single atom considering the coordination environment of the adsorbate. Through our study, we have revealed that stable SAAs are formed in Ni-, Pd-, Pt-based SAAs in the presence of ligands, while Ag-, Au-, Cu- doped with Ni-, Pd-, Pt- lead to aggregation. Finally, we tested our model against several experimental studies and demonstrated its robustness in predicting the formation of SAAs, enabling rapid screening across the vast materials space of SAAs. Additionally, we suggest criteria for stabilization of SAAs, guiding experimental efforts. Overall, our study advances the understanding of thermodynamic stability of colloidal SAAs, paving the way for rational SAA design.

Ionically conducting Li- and Na-phosphonates as organic electrode materials for rechargeable batteries.

Facilitating rapid charge transfer in electrode materials necessitates the optimization of their ionic transport properties. Currently, only a limited number of Li/Na-ion organic cathode materials have been identified, and those exhibiting intrinsic solid-phase ionic conductivity are even rarer. In this study, we present tetra-lithium and sodium salts with the generic formulae: A4-Ph-CH3P and A4-Ph-PhP, wherein A = Li, Na; Ph-CH3P = 2,5-dioxido-1,4-phenylene bis(methylphosphinate); Ph-PhP = 2,5-dioxido-1,4-phenylene bis(phenylphosphinate), as novel alkali-ion reservoir cathode materials. Notably, A4-Ph-PhP exhibits impressive Li-ion and Na-ion conductivities, measured at 2.6 × 10-7 and 1.4 × 10-7 S cm-1, respectively, in a dry state at 30 °C. To the best of our knowledge, these represent the first example of small-molecule organic cathode materials with intrinsic Li+ and Na+ conductivity. Theoretical calculations provide further insight into the electrochemical activity of the Li/Na-phenolate groups, as well as the enhanced electron affinity resulting from -phenyl and -Na substitutions. Additionally, Na4-Ph-PhP displays two distinct charge-discharge plateaus at approximately 2.2 V and 2.7 V, and 2.0 V and 2.5 V vs. Na+/Na, respectively, and demonstrates stable cycling performance, with 100 cycles at a rate of 0.1C and an impressive 1000 cycles at 1C. This study not only expands the portfolio of phenolate-based organic salts for use in metal-ion batteries but also underscores the potential of phosphonate-based organic materials in advancing energy storage technologies.

Best-of-both-worlds computational approaches to difficult-to-model dissociation reactions on metal surfaces.

The accurate modeling of dissociative chemisorption of molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant to modeling heterogeneously catalyzed reactive processes in computational catalysis. The first important scientific challenge in the field is that accurate barriers for dissociative chemisorption are not yet available from first principles methods. For systems that are not prone to charge transfer (for which the difference between the work function of the surface and the electron affinity of the molecule is larger than 7 eV) this problem can be circumvented: chemically accurate barrier heights can be extracted with a semi-empirical version of density functional theory (DFT). However, a second important challenge is posed by systems that are prone to (full or partial) electron transfer from the surface to the molecule. For these systems the Born-Oppenheimer approximation breaks down, and currently no method of established accuracy exists for modeling the resulting effect of non-adiabatic energy dissipation on the dissociative chemisorption reaction. Because two problems exist for this class of reactions, a semi-empirical approach to computing barrier heights, which would demand that computed and experimental dissociative chemisorption probabilities match, is unlikely to work. This Perspective presents a vision on how these two problems may be solved. We suggest an approach in which parameterized density functionals are used as in the previous semi-empirical approach to DFT, but in which the parameters are based on calculations with first principles electronic structure methods. We also suggest that the diffusion Monte-Carlo (DMC) and the random phase approximation (RPA) probably are the best two first principles electronic structure methods to pursue in the framework of the approach that we call first-principles based DFT (FPB-DFT) - providing DMC and the RPA with a steppingstone towards benchmarking and future applications in computational catalysis. Probably the FPB density functional is best based on screened hybrid exchange in combination with non-local van der Waals correlation. We also propose a new electronic friction method called scattering potential friction (SPF) that could combine the advantages and avoid the disadvantages of the two main existing electronic friction approaches for describing non-adiabatic effects: by extracting an electronic scattering potential from a DFT calculation for the full molecule-metal surface system, it might be possible to compute friction coefficients from scattering phase shifts in a computationally convenient and robust fashion. Combining the FPB-DFT and SPF methods may eventually result in barrier heights of chemical accuracy for the difficult-to-model class of systems that are prone to charge transfer. This should also enable the construction of a representative database of barrier heights for dissociative chemisorption on metal surfaces. Such a database would allow testing new density functionals, or, more generally, new electronic structure approaches on a class of reactions that is of huge importance to the chemical industry. Additionally, the difficult-to-model sub-class of systems we focus on is essential to sustainable chemistry and important for a sustainable future. Adding the database envisaged to large databases already existing but mostly addressing gas phase chemistry will enable testing density functionals that have a claim to universality, i.e., to be good for all chemical systems of importance. We also make a suggestion for how to develop such a generally applicable functional, which should have the correct asymptotic dependence of the exchange contribution to the energy in both the gas phase and the metal. Finally we suggest some improvements in the representation of potential energy surfaces and in dynamics methods that would help with the validation of the proposed methods.