Electron Affinity Energy Research Articles

Exploring electron-phonon coupling using quantum computing methods

Abstract Quantum computing in the noisy intermediate-scale quantum (NISQ) era has foregrounded the importance of Variational Quantum algorithms (VQAs). These algorithms are crucial for addressing complex quantum mechanical problems that challenge classical computers. One such problem is the electron-phonon (e-ph) interaction, which is essential for determining the zero-point renormalization (ZPR) of electronic structure properties. The calculation of ZPR of fundamental gap relies on the accurate computation of ionization potential (IP) and electron affinity (EA) energy levels in molecular systems, where the VQAs offer the promising solutions. Despite the critical importance of IP, EA energies and ZPR in quantum chemistry calculations, research into the application of quantum algorithms for these calculations remains limited. To address these challenges, we propose two quantum algorithms for ZPR of fundamental gap calculation using Variational Quantum Deflation (VQD) and Quantum equation of Motion (QEOM) algorithm for several molecular systems. This work opens up new possibilities for the accurate and efficient study of e-ph interaction in electronic structure calculations, even with NISQ-era hardware.

Band Diagram Insights into the Kinetic and Thermodynamic Engineering of Tandem Photocatalytic Cells.

In this work, we theoretically investigate the impact of kinetic and thermodynamic properties on the performance of photocatalytic cells operating in an unassisted tandem configuration, including electron affinity and ionization energies, recombination rates, and reaction rates. To this end, we present general rules and metrics for identifying and isolating the origin of an observed shift in the onset potential at either the photoanode or the photocathode of these devices. The correlation between kinetic and thermodynamic shifts in the onset potential is demonstrated through the use of band diagrams and key comparable features within readily accessible characterization tools: current-voltage plots are taken both under illumination and in the dark and further coupled with Mott-Schottky plots. To illustrate this conceptual framework, a model system comprised of a p-type doped BiVO4 photocathode and an n-type doped BiVO4 photoanode is employed. By varying each of the aforementioned kinetic and thermodynamic parameters in isolation, the manner in which these various mechanisms shift the onset potential is demonstrated. This work intends to showcase how kinetic and thermodynamic effects are distinctly manifested in these commonly used characterization tools and further proposes thermodynamic band-edge engineering as a potentially useful and largely unexplored avenue for possibly improving tandem cell performance, in addition to the conventional approach of optimizing kinetics.

(Invited) Doping at the Extreme in Organic Semiconductors: Challenges and Opportunities

Molecular doping is an effective tool to enhance bulk conductivity, increase carrier injection and de-activate electron or hole traps in organic molecular and polymer semiconductors. Considerable effort has been directed toward the synthesis of powerful and stable p-type and n-type molecular dopants over the past decade.[1,2] This talk reviews a range of molecular redox agents used in organic electronics, with focus on strong reductants and oxidants for organic semiconductors with low electron affinity (EA) and large ionization energy (IE), respectively. In particular, we look at air-stable dimers, e.g. [RuCp*Mes]2, formed of 19-electron organometallic sandwich compounds able to reduce organic semiconductors with EA well below 3 eV.[3] We review powerful single-electron molecular oxidants, e.g. F6-TCNNQ and CN6-CP, which can introduce holes in organic semiconductors with IE larger than 5.6 eV. Applications of these n- and p-dopants to improve the conductivity of carrier injection layers and create large gap semiconductor p-i-n structures are described.[4] The last part of the talk focuses on recent work on adduct-based p-doping of organic semiconductors, applicable to a range of hole transport materials.[5][1]S. Barlow, S.R. Marder, X. Lin, F. Zhang and A. Kahn, Electrical Doping of Organic Semiconductors with Molecular Oxidants and Reductants, Handbook of Conducting Polymers (2019)[2] G. Song, S.B. Kim,S. Mohapatra, Y. Qi, T. Sajoto, A. Kahn, S.R. Marder, S. Barlow, n-Doping of Organic Electronic Materials Using Air-Stable Organometallics, Adv. Mat. 24, 699 (2012)[3] X. Lin, B. Wegner, K. M. Lee, M. A. Fusella, F. Zhang, K. Moudgil, B. P. Rand, S. Barlow, S. R. Marder, N. Kochand A. Kahn, Beating the Thermodynamic Limit: Photo-Activation of n-Doping in Organic Semiconductors, Nature Materials 16, 1209 (2017)[4] H. L. Smith, J. T. Dull, S. Mohapatra, S. Barlow, S. Marder, B. P. Rand, and A. Kahn, Powerful organic molecular oxidant and reductant enable a large gap, blue light-emitting organic homojunction diode, ACS Appl. Mat. Int. 14, 2381 (2022)[5] N. Sakai, R. Warren, F. Zhang, S. Nayak, S. V. Kesava, Y.-H. Lin, H. S. Biswal, X. Lin, A. Kahn, M. Riede, P. K. Nayak and H. J. Snaith, Adduct-based p-doping of Organic Semiconductors, Nature Materials, 20, 1248 (2021)

Improved Energy Density at High Temperatures of FPE Dielectrics by Extreme Low Loading of CQDs.

Electrostatic capacitors, with the advantages of high-power density, fast charging-discharging, and outstanding cyclic stability, have become important energy storage devices for modern power electronics. However, the insulation performance of the dielectrics in capacitors will significantly deteriorate under the conditions of high temperatures and electric fields, resulting in limited capacitive performance. In this paper, we report a method to improve the high-temperature energy storage performance of a polymer dielectric for capacitors by incorporating an extremely low loading of 0.5 wt% carbon quantum dots (CQDs) into a fluorene polyester (FPE) polymer. CQDs possess a high electron affinity energy, enabling them to capture migrating carriers and exhibit a unique Coulomb-blocking effect to scatter electrons, thereby restricting electron migration. As a result, the breakdown strength and energy storage properties of the CQD/FPE nanocomposites are significantly enhanced. For instance, the energy density of 0.5 wt% CQD/FPE nanocomposites at room temperature, with an efficiency (η) exceeding 90%, reached 9.6 J/cm3. At the discharge energy density of 0.5 wt%, the CQD/FPE nanocomposites remained at 4.53 J/cm3 with an efficiency (η) exceeding 90% at 150 °C, which surpasses lots of reported results.

High-throughput phase field simulation and machine learning for predicting the breakdown performance of all-organic composites

All-organic dielectric polymers are materials of choice for modern power electronics and high-density energy storage, and their performance can be significantly improved by doping trace amounts of organic molecular semiconductors with strong electron-affinity energy to suppress charge conduction losses. Insight into the breakdown mechanism of polymers/organic molecular semiconductor composites is essential for the design of high-performance dielectric polymers. This study investigates the impact of the doping concentration of organic molecular semiconductors, dielectric constants, and trap depths on the breakdown performance of dielectric polymers under high temperature and electric fields. A modified phase-field model, incorporating deep traps and carriers’ coulomb capture radius, has been developed to facilitate high-throughput simulations of electrical breakdown in polymer/organic molecular semiconductor composites. This work accurately predicted the breakdown strength of all-organic composites using high-throughput phase-field simulation data as input for machine learning, which provides crucial theoretical support for designing all-organic composite dielectric polymers for energy storage capacitors under extreme conditions.

Efficient and Accurate Estimation of Electronic Polarization Energies for Organic Semiconductors: An Embedding Charge Quantum Mechanics/Continuum Dielectric Model.

Electronic polarization plays a pivotal role in determining the molecular energy levels of organic semiconductors (OSCs) in the condensed phase. However, accurate estimation of the electronic polarization energy is a challenging task due to the intricate imbalance between the precision and efficiency. In this work, we have developed an embedding charge quantum mechanics/continuum dielectric (EC-QM/CD) model, which enables quantitative evaluation of the ionization potential (IP), electron affinity (EA), and polarization energy in both crystalline and amorphous solids for OSCs. The benchmark calculations on both p-type OSCs of oligoacenes and n-type OSCs of A-D-A small-molecule acceptors show that the values of IP, EA, and polarization energy obtained by EC-QM/CD are in good accordance with the experimental measurements or the results by high-precision methods, while the computational costs are substantially reduced. Given its balance between the accuracy and efficiency, the EC-QM/CD model exhibits considerable potential to broaden the applications in the field of OSCs, for instance, high-throughput screening by using solid-state energy levels or polarization energies as critical descriptors.

The Influence of Clustered DNA Damage Containing Iz/Oz and OXOdG on the Charge Transfer through the Double Helix: A Theoretical Study.

The genome-the source of life and platform of evolution-is continuously exposed to harmful factors, both extra- and intra-cellular. Their activity causes different types of DNA damage, with approximately 80 different types of lesions having been identified so far. In this paper, the influence of a clustered DNA damage site containing imidazolone (Iz) or oxazolone (Oz) and 7,8-dihydro-8-oxo-2'-deoxyguanosine (OXOdG) on the charge transfer through the double helix as well as their electronic properties were investigated. To this end, the structures of oligo-Iz, d[A1Iz2A3OXOG4A5]*d[T5C4T3C2T1], and oligo-Oz, d[A1Oz2A3OXOG4A5]*d[T5C4T3C2T1], were optimized at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the aqueous phase using the ONIOM methodology; all the discussed energies were obtained at the M06-2X/6-31++G** level of theory. The non-equilibrated and equilibrated solvent-solute interactions were taken into consideration. The following results were found: (A) In all the discussed cases, OXOdG showed a higher predisposition to radical cation formation, and B) the excess electron migration toward Iz and Oz was preferred. However, in the case of oligo-Oz, the electron transfer from Oz2 to complementary C4 was noted during vertical to adiabatic anion relaxation, while for oligo-Iz, it was settled exclusively on the Iz2 moiety. The above was reflected in the charge transfer rate constant, vertical/adiabatic ionization potential, and electron affinity energy values, as well as the charge and spin distribution. It can be postulated that imidazolone moiety formation within the CDL ds-oligo structure and its conversion to oxazolone can significantly influence the charge migration process, depending on the C2 carbon hybridization sp2 or sp3. The above can confuse the single DNA damage recognition and removal processes, cause an increase in mutagenesis, and harm the effectiveness of anticancer therapy.

The Impact of Substitution of Diphenyl Dialumene on the Molecular Structure and Energetic Properties

The molecular structure, energetic properties, electronic, and vibrational spectroscopy of meta-substituted phenyl dialumene, DPD (Ar–Al=Al–Ar; Ar of the formula C6H5X2, where X = H, CH3, NH2, OH, F, Cl, Br, NO2, and COOH) are investigated by DFT. The singlet states of unsubstituted and substituted DPD adopt trans-planar geometry, while the triplet states adopt non-planar trans-bent geometry. The Al=Al bond length of unsubstituted DPD-H in a singlet state is calculated to be 2.734 Å, and there is no systematic and significant change upon substitution (2.734–2.744 Å). The substitution affects the absolute energy, ionization potential, electron affinity, and reorganization energy. The wavelength of maximum absorbance of DPD-H is determined to be 443 nm, and the substitute analogues DPD-X (X = OH, F, Cl, Br, NO2, CHO, COOH) show a hypsochromic shift, while DPD-CH3 and DPD-NH2 exhibit a bathochromic effect. The HOMO to LUMO+1 transition is the major transition for the meta-substituted DPD, except for X=NO2, where the transition is to LUMO+2. Considering the reorganization energy values, meta-substituted DPD can be useful as hole transporters. In addition, the theoretical data will aid in predicting the behavior of this class of compounds, facilitating the design and synthesis of similar compounds with desired properties.

Constructing Deep Traps to Achieve Excellent Dielectric Properties in Crystal-Based HfO2/PEI Nanocomposite Films with Ultralow Filler Loadings.

Mixing fillers featured with wide band gaps in polymers can effectively meet the requirement of higher energy storage densities. However, the fundamental relationship between the crystal structures of fillers and the dielectric properties of the corresponding nanocomposites is still unclear. Accordingly, we introduced ultralow contents of the synthesized cubic Hafnium dioxide (c-HfO2) or monoclinic Hafnium dioxide (m-HfO2) as deep traps into poly(ether imide) (PEI) to explore their effects on dielectric properties and the charge-blocking mechanism. m-HfO2/PEI showed better charge trapping due to the higher electron affinity and deeper trap energy. At room temperature, the 0.4 vol % m-HfO2/PEI maintains an ultralow dielectric loss of 0.008 while obtaining a dielectric constant twice that of pure PEI at 1 kHz, simultaneously outperforming in terms of leakage current density, breakdown strength (452 kV mm-1), discharge energy density (Ud, 5.03 J cm-3), charge-discharge efficiency (η, 92%), and dielectric thermal stability. At 125 °C, it exhibits a considerable Ud of 2.48 J cm-3 and a high η of 85% at 300 kV mm-1, surpassing the properties of pure PEI. This promising work opens up a new path for studying HfO2-derived dielectrics with unique crystal structures.

Tenability on schiff base Hydrazone derivatives and Frontier molecular orbital

Context hydrazine compounds based on 1,3,5-triazine were synthesised and their molecular structures were characterised by elemental analysis, Electronic, IR and 1H NMR spectra. The spectral behaviour of the newly prepared compounds in organic solvents of different polarities was extensively studied and correlated to the molecular structure. In this study, 1,3,5-Triazine derivatives (L1, L6, L7, L8) have been subjected to theoretical studies using the Semi-empirical PM3 quantum chemical method. The physical-chemical properties of some Hydrazone derivatives are determined theoretically. The molecular geometry, the Highest Occupied Molecular Orbital (HOMO) - Lowest Unoccupied Molecular Orbital (LUMO) energy gap, molecular hardness (η), ionisation energy (IE), Electron affinity and total energy were analysed, and applications as biological effects were done.

<i>Ab initio</i> molecular dynamics study on dissociation process of 2-thiouracil and its tautomers under low-energy electron interactions

When biomolecules interact with high-energy particles and rays, they are directly ionized or dissociated, then a large number of low-energy electrons are formed as secondary particles. These low-energy electrons will attach to biomolecules, and trigger off the secondary dissociation, forming free radicals and ions with high reactivity, which can damage the structure and function of the biomolecule and cause irreversible radiation damage to the biomolecule. It is important to study the low-energy dissociative electron attachment (DEA) process of biomolecules for understanding radiation damage to biological organisms. Currently, the theoretical studies of DEA have mainly focused on the bound states of negative ions and the types of resonances in the dissociation process. The dissociation process is well described by quantum computational method, but the diversity and complexity of dissociation channels present in the dissociation process of 2-thiouracil molecule also pose a great computational challenge to these methods. In addition, the quantum computational methods are not ideal for dealing with the discrete states of chemical bonds and the problem of continuity coupling of electrons. The dissociation dynamics of biomolecules mainly results from ionization and electron attachment. <i>Ab initio</i> molecular dynamics simulation can reasonably describe these processes. In light of these considerations, <i>ab initio</i> molecular dynamics simulation is used in this work to study dynamic variation process in DEA. The low-energy electron dissociative attachment to 2-thiouracil in the gas phase is studied by using the Born-Oppenheimer molecular dynamics model combined with density functional theory. It is found that an important dehydrogenation phenomenon of 2-thiouracil and its tautomers occurs in the DEA process, and that the N—H and C—H bond are broken at specific locations. Due to the loss of hydrogen atoms at the N and C sites, the closed-shell dehydrogenated negative ion (TU-H)<sup>–</sup> forms, which is the most important negative ion fragments in the dissociation process. The potential energy curves, the bond dissociation energy and the electron affinity energy of the broken bond show that the N—H bond is the most likely to break, indicating the formation of the negative ion (TU-H)<sup>–</sup> mainly comes from the breaking of N—H bond. The theoretical calculations in this work are in good agreement with the available experimental results, indicating that the chosen calculation method is fully reliable. ​The BOMD simulations can not only dynamically recover the process of dissociative attachment of low-energy electrons to 2-thiouracil, but also more importantly provide an insight into the mechanisms of dehydrogenation and dissociation channels of 2-thiouracil molecules in DEA process.

N‐Doping Effects On Electrocatalytic Water Splitting of Non‐Noble High‐Entropy Alloy Nanoparticles Prepared by Inert Gas Condensation

AbstractThe unique catalytic activities of high‐entropy alloys (HEAs) emerge from the complex interaction among different elements in a single‐phase solid solution. As a “green” nanofabrication technique, inert gas condensation (IGC) combined with laser source opens up a highly efficient avenue to develop HEA nanoparticles (NPs) for catalysis and energy storage. In this work, the novel N‐doped non‐noble HEA NPs are designed and successfully prepared by IGC. The N‐doping effects of HEA NPs on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are systematically investigated. The results show that N‐doping is conducive to improving the OER, but unfavorable for HER activity. The FeCoNiCrN NPs achieve an overpotential of 269.7 mV for OER at a current density of 10 mA cm−2 in 1.0 M KOH solution, which is among the best reported values for non‐noble HEA catalysts. The effects of the differences in electronegativity, ionization energy and electron affinity energy among mixed elements in N‐doped HEAs are discussed as inducing electron transfer efficiency. Combined with X‐ray photoelectron spectroscopy and the extended X‐ray absorption fine structure analysis, an element‐design strategy in N‐doped HEAs electrocatalysts is proposed to improve the intrinsic activity and ameliorate water splitting performance.

Molecular Orbital Properties and Insulation Characteristics of Flaxseed Oil

This study aims to analyze the molecular orbital parameters of flaxseed oil (linum usitatissimum) and to measure the AC breakdown voltages at different electrode gaps with various rate of rises. AC breakdown voltages of flaxseed oil are measured at 1.0 and 2.5 mm electrode settings with 0.5 kV/s, 2.0 kV/s and 3.0 kV/s rate of rises, adhering to IEC and IEEE standards. UV-VIS (Ultraviolet–Visible) and FT-IR (Fourier Transform-Infrared) measurement tests carried out after breakdown voltage measurements reveals that the molecular structure of the oil remains stable against electrical discharges. The compounds of flaxseed oil are analyzed using GC-MS and it is determined that the oil mainly consists of seven triglycerides in accordance with the literature. In order to better understand the electrical behavior of these triglycerides, molecular orbital properties such as ionization potential, electron affinity and electron energy gap are analyzed employing Density Functional Theory (DFT) using B3LYP/6-311 + G(d,p) and B3PW91/6-311 + G(d,p) basis sets. The advantages of flaxseed oil such as AC dielectric strength, stability against breakdown mechanism, homogeneous molecular electrical characteristics of its compounds and antioxidant content make this oil as one of the potential natural ester alternatives to mineral oils in the power system industry.

A systematic improvement to UGA-SSMRCCSD equations and its implication for potential energy curves.

The Unitary Group Adaptation (UGA) offers a very compact and efficient spin adaptation strategy for any spin-free Hamiltonian in a many body framework. Our use of UGA in the context of state-specific (SS) Jeziorski-Monkhorst Ansatz based multireference coupled cluster (MRCC) theory obviates the non-commutativity between the spin-free cluster operators via a normal ordered exponential parametrization in the wave operator. A previous formulation of UGA-SSMRCC by us [R. Maitra, D. Sinha, and D. Mukherjee, J. Chem. Phys. 137, 024105 (2012)], using the same ansatz, employed certain sufficiency conditions to reach the final working equations, which cannot be improved systematically. In this article, we will present a more rigorous formulation that follows from an exact factorization of the unlinked terms of the Bloch equation, resulting in equations on which a hierarchy of approximations can be systematically performed on the emergent additional terms. This derivation was shown in our recent article [D. Chakravarti, S. Sen, and D. Mukherjee, Mol. Phys. 119, e1979676 (2021)] in the context of a single open shell CC formalism and was applied to spectroscopic energy differences where the contribution of the new terms was found to be of the order of ∼0.001eV for ionization potential, electron affinity, and excitation energy. In the current work, we will present a comparison between the earlier and current formulations via both a theoretical analysis and a numerical demonstration of the dramatic effect of the additional terms brought in by the factorization on potential energy curves. The contribution of such terms was found to gain importance with an increase in the number of singly occupied active orbitals in the model space functions.

Interpretable delta-learning of GW quasiparticle energies from GGA-DFT

Accurate prediction of the ionization potential and electron affinity energies of small molecules are important for many applications. Density functional theory (DFT) is computationally inexpensive, but can be very inaccurate for frontier orbital energies or ionization energies. The GW method is sufficiently accurate for many relevant applications, but much more expensive than DFT. Here we study how we can learn to predict orbital energies with GW accuracy using machine learning (ML) on molecular graphs and fingerprints using an interpretable delta-learning approach. ML models presented here can be used to predict quasiparticle energies of small organic molecules even beyond the size of the molecules used for training. We furthermore analyze the learned DFT-to-GW corrections by mapping them to specific localized fragments of the molecules, in order to develop an intuitive interpretation of the learned corrections, and thus to better understand DFT errors.

Study on the influence of chain extension and substituent position on charge transport properties and optoelectronic properties based on 2,5-di(pyrazine-2-yl)furan derivatives

In this paper, the basic structure of 2,5-di(pyrazine-2-yl)furan (DPF) was initially designed to tune the charge transport properties and photoelectric properties of organic materials by chain extension. Through the calculation of recombination energy, the structure with the introduction of anthracene group (DPF-A) is a stable P-type material with the smallest recombination energy in terms of adiabatic ionization potential, so the chain extended molecule DPF-A was selected as the base for the study of substituent positions. While thiophene, trifluorinated acyl, and methoxy groups were introduced to design DPF-A series derivatives. Density functional theory with high computational accuracy was applied to investigate geometric structure, orbital energy levels, ionization energy, electron affinity energy, and recombination energy. The results show that the increase (decrease) of the HOMO (LUMO) energy level leads to the red (blue)-shift of absorption wavelength and fluorescence emission wavelength; the vertical ionization potential decreases and the vertical electron affinity potential increases, thus the hole and electron injection barrier decreases; the decrease of the hole/electron recombination energy improves the charge transport ability of the molecule. Moreover, the adjustment of thiophene orientation and the position of the introduced group has the potential to transform the p-type material into an n-type material, resulting in the enhanced electron injection ability.

A Simple Strategy to Design Polycyclic Superhalogens.

Polycyclic hydrocarbon (PH) radicals and anions such as C9H7-, C11H7-, C13H9-, and C15H9- generally possess low electron affinity (EA) and vertical detachment energy (VDE), respectively, due to their aromaticity and, consequently, enhanced stability. In this work, we propose a simple strategy to design polycyclic superhalogens (PSs) by replacing all hydrogens by cyano (CN) groups. Superhalogens can be defined as the radicals having higher EA than halogens or anions having higher VDE than halides (3.64 eV). Our density functional calculations suggest that the EA (VDE) of PS radicals (anions) exceeds 5 eV. All these PS anions are aromatic, except C11(CN)7-, which is anti-aromatic. The superhalogen property of these PSs can be attributed to the EA of CN ligands, leading to the delocalization of extra electronic charge significantly as explained using prototype C5H5-x(CN)x systems. We also notice that the 'superhalogenity' (superhalogen behavior) of C5H5-x(CN)x- is directly related to their aromaticity. We have also shown that the substitution of CN is energetically favorable, which confirms their experimental viability. Our findings should motivate experimentalists to synthesize these superhalogens for further exploration and future applications.

Machine Learning for the Prediction of Ionization Potential and Electron Affinity Energies Obtained by Density Functional Theory

AbstractQuantum chemical (QC) calculations based on density functional theory (DFT) provide increasingly accurate estimates of various properties, but with a relatively high computational cost. Machine learning (ML) techniques can be envisaged to extract new knowledge from these large volumes of data, creating empirical models to fast predict QC calculations in new situations. Here, ML algorithms were explored for the fast estimation of ionization potential (IP) and electron affinity (EA) energies calculated by DFT using the B3LYP and PBE0 with 6–31G** basic set on molecular descriptors generated from DFT‐optimized geometries. A database of 9,410 and 9,627 small organic structures for IP and EA energies modelling were used, respectively. Several ML algorithms such as random forest, support vector machines, deep learning multilayer perceptron networks, and light gradient‐boosting machine were screened. The best performance was achieved with a consensus regression model predicted an external test set of 972 and 963 small organic molecules achieving a mean absolute error up to 0.23 eV and 0.32 eV for modelling IP and EA energies, respectively.

The Influence of 5',8-Cyclo-2'-Deoxyguanosine on ds-DNA Charge Transfer Depends on Its Diastereomeric Form: A Theoretical Study.

The genetic information stored in the nucleobase sequence is continuously exposed to harmful extra- and intra-cellular factors, which can lead to different types of DNA damage, with more than 70 lesion types identified so far. In this article, the influence of a multi-damage site containing (5'R/S) 5',8-cyclo-2'-deoxyguanosine (cdG) and 7,8-dihydro-8-oxo-2'-deoxyguanosine (OXOdG) on charge transfer through ds-DNA was taken into consideration. The spatial geometries of oligo-RcdG: d[A1(5'R)cG2A3OXOG4A5]*d[T5C4T3C2T1] and oligo-ScdG: d[A1(5'S)cG2A3OXOG4A5]*d[T5C4T3C2T1] were optimized at the M06-2X/6-D95**//M06-2X/sto-3G level of theory in the aqueous phase using ONIOM methodology. For all the electronic property energies under discussion, the M06-2X/6-31++G** level of theory was used. Additionally, the non-equilibrated and equilibrated solvent-solute interactions were into consideration. The obtained results confirm the predisposition of OXOdG to radical cation formation regardless of the presence of other lesions in a ds-DNA structure. In the case of electron transfer, however, the situation is different. An excess electron migration towards (5'S)cdG was found to be preferred in the case of oligo-ScdG, while in the case of oligo-RcdG, OXOdG was favored. The above observation was confirmed by the charge transfer rate constant, vertical/adiabatic ionization potential, and electron affinity energy values, as well as the charge and spin distribution analysis. The obtained results indicate that 5',8-cyclo-2'-deoxyguanosine, depending on the C5' atom chirality, can significantly influence the charge migration process through the double helix. The above can be manifested by the slowdown of DNA lesion recognition and removal processes, which can increase the probability of mutagenesis and subsequent pathological processes. With regard to anticancer therapy (radio/chemo), the presence of (5'S)cdG in the structure of formed clustered DNA damage can lead to improvements in cancer treatment.

Understanding the hydrogen evolution reaction activity of doped single-atom catalysts on two-dimensional GaPS4 by DFT and machine learning

As a zero-carbon fuel, hydrogen can be produced via electrochemical water splitting using clean electric energy by the hydrogen evolution reaction (HER) process. The ultimate goal of HER catalyst is to replace the expensive Pt metal benchmark with a cheap one with equivalent activities. In this work, we investigated the possibility of HER process on single-atom catalysts (SACs) doped on two-dimensional (2D) GaPS4 materials, which have a large intrinsic band gap that can be regulated by doping and tensile strain. Based on the machine learning regression analysis, we can expand the prediction of HER performance to more catalysts without expensive DFT calculation. The electron affinity and first ionization energy are the two most important descriptors related to the HER behavior. Furthermore, constrain molecular dynamics with solvation models and constant potentials were applied to understand the dynamics barrier of HER process of Pt SAC on GaPS4 materials. These findings not only provide important insights into the catalytic properties of single-atom catalysts on GaPS4 2D materials, but also provides theoretical guidance paradigm for exploration of new catalysts.