Low-energy Transitions Research Articles

Investigating the role of smart technologies, financial, and environmental innovations in tackling the ecological sustainability: a global pathway toward low carbon energy transition.

Since the beginning of the twenty-first century, the rapid development of modern technologies has brought unprecedented social prosperity to mankind as technologies penetrate every sector of the economy. These technologies have given a new dimension to the energy sector. The key purpose of this study is to investigate the crucial impact of technological revolutions, namely, smart grids, smart devices, financial innovations, and environmental innovations, on greenhouse gas emissions (GHGs). To this end, the study utilized data from European, Asian, Middle Eastern, and African countries and employed first- and second-generation methods, such as DOLS, FMOLS, and CS-ARDL models. The research shows that smart grids are the only factor in reducing GHGs, regardless of geographic division. Hence, linking smart grid resources to climate change goals requires short-term deployment strategies with a clear long-term vision and the fundamental goal of transforming the power structure into a net zero-emission system. The study also demonstrates that the emergence of ICT in electricity consumption has not yet reached a level that can promote environmental excellence. The study documented the critical role of financial innovation and environmental innovation in addressing environmental degradation.

Melting-free integrated photonic memory with layered polymorphs

Abstract Chalcogenide-based nonvolatile phase change materials (PCMs) have a long history of usage, from bulk disk memory to all-optic neuromorphic computing circuits. Being able to perform uniform phase transitions over a subwavelength scale makes PCMs particularly suitable for photonic applications. For switching between nonvolatile states, the conventional chalcogenide phase change materials are brought to a melting temperature to break the covalent bonds. The cooling rate determines the final state. Reversible polymorphic layered materials provide an alternative atomic transition mechanism for low-energy electronic (small domain size) and photonic nonvolatile memories (which require a large effective tuning area). The small energy barrier of breaking van der Waals force facilitates low energy, fast-reset, and melting-free phase transitions, which reduces the chance of element segregation-associated device failure. The search for such material families starts with polymorphic In2Se3, which has two layered structures that are topologically similar and stable at room temperature. In this perspective, we first review the history of different memory schemes, compare the thermal dynamics of phase transitions in amorphous-crystalline and In2Se3, detail the device implementations for all-optical memory, and discuss the challenges and opportunities associated with polymorphic memory.

Electron-donating functional groups strengthen ligand-induced chiral imprinting on CsPbBr3 quantum dots

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 CsPbBr3 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.

Optimal balance: alkali metal-doped boron carbide nanosheets achieve superior stability and nonlinear optical responsiveness.

Nonlinear optical (NLO) materials play a vital role in various technological domains, including optoelectronics and photonic devices. Designing NLO materials, particularly inorganic ones, that strike a compromise between nonlinear optical sensitivity and stability has always been a difficult task. In order to improve the stability and NLO responsiveness, we propose and examine alkali metal-doped boron carbide nanosheets (M@BCNs) in this study. Calculated interaction energies (E int), which span from -65.5 to -94.9 kcal mol-1, show the stability of the M@BCN complexes. The first hyperpolarizability value has also increased, to a maximum of 3.11 × 105 au, indicating improved nonlinear optical characteristics. QTAIM (quantum theory of atoms in molecules) and NCI (non-covalent interactions) analyses demonstrate the validity of the interactions. According to NBO (natural bond orbital) analysis, the alkali metals gain almost +1 charge. Due to the low transition energies and considerable charge transfer between the alkali metals and nanosheet, the nonlinear optical response is significantly improved. The M@BCN complexes also show transparency in the ultraviolet region, with absorption maxima ranging from 917 to 2788 nm. This study proposes a viable approach for developing alkali metal-doped boron carbide nanosheets with improved NLO response and stability.

From loose to tight: unveiling bond stretch isomerism in π-complexes of Li, Na and K.

The study investigates the phenomenon of bond stretch isomerism (BSI) in complexes formed between alkali metals (Li, Na, K) and various non-aromatic, aromatic hydrocarbons, as well as heteroaromatic systems. The research employs density functional theory (DFT) calculations to optimize complex geometries and analyze their electronic structures using molecular electrostatic potential (MESP), charge, and spin density analyses. The results reveal that these complexes can exist in two distinct configurations: 'loose' long-bond isomers (lbi) that retain the original hydrocarbon geometry and 'tight' short-bond isomers (sbi) that undergo geometrical distortion upon complexation, with sbi generally being more stable. The interconversion between lbi and sbi occurs through a transition state. The study highlights the crucial role of electron transfer in BSI, with sbi involving valence electron transfer from the metal to the hydrocarbon, leading to zwitterionic radical complexes. In contrast, lbi exhibit a slight electron density transfer from the hydrocarbon to the metal. The presence of low-energy transition states between lbi and sbi suggests a dynamic shuttling mechanism for alkali metals, particularly Li, on hydrocarbon surfaces. The study identifies Li complexes as potential candidates for anode materials in batteries due to their stability and electron transfer properties, offering valuable insights into the design of advanced materials for energy storage applications.

Which energy citizenship in positive energy districts? A governmentality social psychological analysis of participatory governance

ABSTRACT Towards low carbon energy transitions, the EU is developing Positive Energy Districts (PEDs) which produce more renewable energy than they consume. This implies more participatory governance which decentralises and democratises energy decisions to citizens, as captured in the emergent concept of ‘energy citizenship’. However, it has been argued that these governmental strategies and the energy citizens they create have been co-opted by a neoliberal governmentality. This may limit citizens’ rights and responsibilities as only consumers/prosumers in the private sphere. However, the neoliberal form of energy citizenship as well as potential alternative forms have seldom been empirically examined, so the main aim of this paper is to analyse which representations of energy citizenship are fostered in PED policies at EU, national, and local levels in a case study of Torres Vedras, Portugal. The analysis, which combines a governmentality approach with the critical social psychology of citizenship, unveils neoliberal energy citizenship as the hegemonic representation in these policies, and identifies emancipated representations of energy citizenship based on entrepreneurial energy activism and energy localism.

FinTech and sustainable financing for low carbon energy transitions: A biodiversity and natural resource perspective in BRICS economies

BRICS countries grapple with formidable challenges, declining biodiversity, and energy crises. This study examines the transformative potential of financial technology and sustainable financing in driving low-carbon energy transitions. It aims to achieve two objectives: first, to investigate the effectiveness of FinTech and sustainable financing in driving low-carbon energy transitions; and second, to probe the relationship between these mechanisms and the imperatives of biodiversity and sustainable natural resource utilization in the context of BRICS economies. Through the application of advanced econometric techniques such as fully modified OLS (FMOLS), dynamic OLS (DOLS), fixed effect-OLS (FE-OLS), and Method of Moments Quantile Regression (MMQR), this study investigates the impact of FinTech, sustainable financing, and biodiversity and natural resource utilization on low-carbon energy transitions. Our empirical findings underscore a robust, long-term co-integrating relationship among low-carbon energy advancement, financial technology, financial development, biodiversity preservation, and natural resource utilization. Notably, both FinTech innovations and accessible sustainable financing mechanisms positively influence the adoption of low-carbon energy practices. Moreover, economies rich in biodiversity and with higher income levels exhibit a strong inclination toward low-carbon energy sources. However, overreliance on natural resource extraction hampers the sustained adoption of low-carbon energy practices. This study recommends strategies that leverage FinTech and sustainable financing, while emphasizing the importance of safeguarding natural resources and promoting environmental management. These measures effectively address the energy crisis and foster policies and practices for low-carbon energy transitions.

The role of nuclear energy in low carbon energy transition: evidence from panel data approach in EU.

The aim of this study is to employ panel data approach to investigate determinants of total GHG emissions in all European Union (EU) economies in years 1990-2018 and evaluate the role of nuclear energy in climate change mitigation. It incorporates the following variables potentially affecting the greenhouse gas (GHG) emissions: economic-gross domestic product (GDP) per capita and GDP per capita squared to control for non-linear relationship between economic output and GHG emissions; structural-economic structure reflected in the share of manufacturing in total gross value added (GVA); energy-mix-share of nuclear power and renewable sources in total gross electricity production; environmental policy-the amount of environmental taxes (as a percentage of GDP) and the number of European Union Emission Trading System (EU ETS) allowances auctioned or sold (as a percentage of GDP per capita). The main findings of this study confirm the long-run relationship between GHG emissions, GDP level, and energy-mix variables. It endorses that higher share of nuclear power together with renewables in gross electricity production has significant impact on GHG emissions in the long run. In turn, it also validates the existence of the environmental Kuznets curve for selected countries.

Hexaguanidino-Triptycenes and Triphenylenes: Electronic Coupling in Molecules Containing Three Redox-Active o-Diguanidinobenzene Units Connected either Directly or Interacting Through Homoconjugation.

Novel redox-active hexaguanidine molecules with multiple redox states were synthesized by connecting three o-diguanidinobenzene units. In 2,3,6,7,14,15-hexaguanidino-triptycenes, the three redox-active o-diguanidinobenzene units are connected through C-C bonds to the sp3 -hybridized bridgehead C atoms, and in 2,3,6,7,10,11-hexaguanidino-triphenylenes they are directly connected. The connectivity difference leads to different electronic coupling between the three redox-active o-diguanidinobenzene units, with homoconjugation being present in the triptycene, but not in the triphenylene compounds. Motivated by the appearance of an intense low-energy electronic transition, we especially analysed the effect of homoconjugation on the electronic structure and charge delocalization in the dicationic redox state of the triptycene derivatives. Then, several trinuclear high-spin cobalt (and copper) complexes were synthesized with the triphenylene and triptycene ligands, and the magnetic coupling and redox properties analysed. By choice of the coligands (hexafluoroacetylacetonate, trifluoroacetylacetonate and acetylacetonate), oxidation could be switched between metal- and ligand-centered redox events, leading to drastic changes in the magnetic or optical properties, especially as a consequence of homoconjugation in the triptycene derivatives.

Review on measurement-based frequency dynamics monitoring and analyzing in renewable energy dominated power systems

The massive integration of clean energy and renewable energy source (RES) is one of the most important trends in the low carbon energy transition toward carbon neutrality. Such an important goal significantly alters the power system dynamic behavior. Consequently, monitoring and analyzing the complex frequency dynamic of RES-dominated power systems play an essential role in ensuring power system security and stability. The measurements, especially those supported by wide area measurement systems (WAMSs), can enable full state awareness and deep informatization of the power system and therefore provide effective solutions for monitoring and analyzing system frequency dynamic behaviors with complex features. This paper focus on the application of measurements in monitoring and modeling analysis technologies for the features of frequency dynamics of RES-dominated power systems. We summarize related research on online monitoring of frequency dynamic behavior features based on the information from measurements. Further, for system frequency security assessment, measurements can improve the traditional methods and promote new data-driven methods for more accuracy and effective frequency dynamics analysis. Finally, future directions and possible solutions for measurement-based frequency dynamics monitoring and analyzing are prospected.

Band-Edge Energy Levels of Dynamic Excitons in Cube-Shaped CdSe/CdS Core/Shell Nanocrystals.

An electron-hole pair in a cube-shaped CdSe/CdS core/shell nanocrystal exists in the form of dynamic excitons across the strongly and weakly confined regimes under ambient temperatures. Photochemical doping is applied to distinguish the band-edge electron and hole levels, confirming an effective mass model with universal constants. Reduction of the optical bandgap upon epitaxy of the CdS shells is caused by lowering the band-edge electron level and barely affecting the band-edge hole level. Similar shifts of the electron levels, yet retaining the hole levels, can switch the order in energy of the three lowest-energy transitions. Thermal distribution of 1-4 electrons among the two thermally accessible electron levels follows number-counting statistics, instead of Fermi-Dirac distribution.

Theoretical study of an N-heterocyclic carbene-catalyzed annulation reaction between an enal and a β-silyl enone: Mechanism and origin of stereoselectivity

In this study, the mechanism and origin of the stereoselectivity of an N-heterocyclic carbene (NHC)-catalyzed transformation reaction between an enal and a β-silyl enone are systematically investigated using density functional theory (DFT) at the M06-2X level. Multiple pathways are proposed and studied to identify the most energetically favorable mechanism for the reaction. The calculation results show that the most energetically favorable pathway comprises the following processes: nucleophilic addition of NHC to the Si-face of the enal to form a zwitterionic intermediate, two sequential CsHCO3-assisted intramolecular proton shifts to produce an enolate intermediate, Michael-type addition of the enolate intermediate to the β-silyl enone, ring closure to construct a six-membered ring intermediate, and the dissociation of NHC to release the final product. The reaction between the enolate intermediate and the β-silyl enone is identified as the stereoselectivity-determining step, preferentially generating an RS-configured product. Subsequent atoms-in-molecules (AIM) and noncovalent interaction (NCI) analyses verify that the main factor for inducing stereoselectivity is the higher number of noncovalent intermolecular interactions in the low-energy transition state.

Interrelated effects of age and parenthood on whole-brain controllability: protective effects of parenthood in mothers.

Controllability is a measure of the brain's ability to orchestrate neural activity which can be quantified in terms of properties of the brain's network connectivity. Evidence from the literature suggests that aging can exert a general effect on whole-brain controllability. Mounting evidence, on the other hand, suggests that parenthood and motherhood in particular lead to long-lasting changes in brain architecture that effectively slow down brain aging. We hypothesize that parenthood might preserve brain controllability properties from aging. In a sample of 814 healthy individuals (aged 33.9 ± 12.7 years, 522 females), we estimate whole-brain controllability and compare the aging effects in subjects with vs. those without children. We use diffusion tensor imaging (DTI) to estimate the brain structural connectome. The level of brain control is then calculated from the connectomic properties of the brain structure. Specifically, we measure the network control over many low-energy state transitions (average controllability) and the network control over difficult-to-reach states (modal controllability). In nulliparous females, whole-brain average controllability increases, and modal controllability decreases with age, a trend that we do not observe in parous females. Statistical comparison of the controllability metrics shows that modal controllability is higher and average controllability is lower in parous females compared to nulliparous females. In men, we observed the same trend, but the difference between nulliparous and parous males do not reach statistical significance. Our results provide strong evidence that parenthood contradicts aging effects on brain controllability and the effect is stronger in mothers.

Amide isomerization pathways: Electronic and structural background of protonation- and deprotonation-mediated cis-trans interconversions.

The cis-trans isomerization of amide bonds leads to wide range of structural and functional changes in proteins and can easily be the rate-limiting step in folding. The trans isomer is thermodynamically more stable than the cis, nevertheless the cis form can play a role in biopolymers' function. The molecular system of N-methylacetamide · 2H2O is complex enough to reveal energetics of the cis-trans isomerization at coupled cluster single-double and coupled cluster single-double and perturbative triple [CCSD(T)] levels of theory. The cis-trans isomerization cannot be oversimplified by a rotation along ω, since this rotation is coupled with the N-atom pyramidal inversion, requesting the introduction of a second dihedral angle "α." Full f(ω,α) potential energy surfaces of the different amide protonation states, critical points and isomerization reaction paths were determined, and the barriers of the neutral, O-protonated and N-deprotonated amides were found too high to allow cis-trans interconversion at room temperature: ∼85, ∼140, and ∼110 kJ mol-1, respectively. For the N-protonated amide bond, the cis form (ω = 0°) is a maximum rather than a minimum, and each ω state is accessible for less than ∼10 kJ mol-1. Here we outline a cis-trans isomerization pathway with a previously undescribed low energy transition state, which suggests that the proton is transferred from the more favorable O- to the N-protonation site with the aid of nearby water molecules, allowing the trans → cis transition to occur at an energy cost of ≤11.6 kJ mol-1. Our results help to explain why isomerase enzymes operate via protonated amide bonds and how N-protonation of the peptide bond occurs via O-protonation.

Entanglement harvesting for different gravitational wave burst profiles with and without memory

In the present article, we study how different gravitational wave (GW) burst profiles in linearized gravity, with and without the asymptotic memory, may influence the harvesting between two static Unruh-DeWitt detectors. To this end, we investigate the following burst profiles — Gaussian, sech-squared, Heaviside step function, and tanh. Out of these, the first two bursts contain no memory, while the latter two consist of a non-vanishing memory effect. We find that in all of these cases, entanglement harvesting is possible, and it decreases with the increasing distance between detectors and the detector transition energy. We observe that the harvesting differs qualitatively based on the presence or absence of the memory, which is prominent in a low transition energy regime. With memory, the harvesting keeps increasing with decreasing transition energy, while without memory, it tends to reach finite values. Furthermore, for the two burst profiles without memory, longer bursts correspond to greater harvesting in the low detector transition energy regime, and this characteristic is reversed for larger transition energy. Meanwhile, for the tanh-type profile with memory, harvesting is always greater for shorter bursts. We discuss various implications of our findings.

Digital inclusive finance and energy transition towards carbon neutrality: Evidence from Chinese firms

Given the ongoing digitalization process in financial sector, the interaction between the energy transition and digital inclusive finance (DIF) can potentially affect the decarbonization process towards carbon neutrality. This paper utilizes an unbalanced panel data of Chinese firms spanning from 2011 to 2015 to estimate the impact of DIF on firms' low carbon energy transition with a fixed-effect model. The findings reveal that the development of DIF has a significantly negative effect on firms' consumption of fossil fuels. These findings remain robust even after employing a series of robustness tests and implementing an instrumental variable approach to address potential endogeneity concerns. Investigations of the underlying mechanism reveal that DIF primarily promotes the energy transition by increasing firms' investment in information and communications technology (ICT) and green technologies. Moreover, DIF plays a particularly significant role in promoting the energy transition of non-state-owned firms, small firms, non-energy-intensive firms, and firms in the eastern region. This paper suggests leveraging the positive role of DIF in the energy transition of firms, especially by encouraging firms to invest in sustainable technologies to accelerate their energy transition. Furthermore, it emphasizes the need for coordinated development of DIF in different regions and addresses the imbalance in firms' energy transition across these regions.

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4

The tetraoxido ruthenium(VIII) radical cation, [RuO4 ]+ , should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO4 ]+ , produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO4 ]+ is identified by the chemical shift at the ruthenium M3 edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO4 ]+ to the closed-shell [RuO4 H]+ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO4 ]+ than for [OsO4 ]+ .

Trimetallic CoAuPd alloy nanoparticles confined in mesoporous MIL-101 with low transition energy for enhanced hydrogen generation from formic acid

Developing efficient and low-cost catalysts with excellent hydrogen generation from formic acid (FA) is highly desired but challenging. Herein, a uniform CoAuPd alloy nanoparticles (NPs) were successfully confined into MIL-101 by a surfactant-free co-reduction method. The elevated stability of Co0 in the protected alloy NPs makes its application in FA dehydrogenation successful. Significantly, the resulting Co0.3Au0.35Pd0.35/MIL-101 composites with the lower consumption of noble metals exhibit the 100% hydrogen selectivity, highest activity and excellent stability toward hydrogen generation from FA without any additive at room temperature. Theoretical results reveal that the enhanced hydrogen generation from FA can be ascribed to the synergistic effects between CoAuPd alloy NPs and MIL-101 frameworks with lowest transition energy between LUMO and HOMO and highest adsorption energy of FA, as compared to the bimetallic alloy NPs. Therefore, the present results open up new avenues for developing cost effective and high-performance catalysts for the generation of hydrogen from FA by using porous MOFs as hosts for non-noble metal based NPs.

Understanding the Optical Properties of Doped and Undoped 9-Armchair Graphene Nanoribbons in Dispersion.

Graphene nanoribbons are one-dimensional stripes of graphene with width- and edge-structure-dependent electronic properties. They can be synthesized bottom-up in solution to obtain precise ribbon geometries. Here we investigate the optical properties of solution-synthesized 9-armchair graphene nanoribbons (9-aGNRs) that are stabilized as dispersions in organic solvents and further fractionated by liquid cascade centrifugation (LCC). Absorption and photoluminescence spectroscopy reveal two near-infrared absorption and emission peaks whose ratios depend on the LCC fraction. Low-temperature single-nanoribbon photoluminescence spectra suggest the presence of two different nanoribbon species. Based on density functional theory (DFT) and time-dependent DFT calculations, the lowest energy transition can be assigned to pristine 9-aGNRs, while 9-aGNRs with edge-defects, caused by incomplete graphitization, result in more blue-shifted transitions and higher Raman D/G-mode ratios. Hole doping of 9-aGNR dispersions with the electron acceptor F4TCNQ leads to concentration dependent bleaching and quenching of the main absorption and emission bands and the appearance of red-shifted, charge-induced absorption features but no additional emission peaks, thus indicating the formation of polarons instead of the predicted trions (charged excitons) in doped 9-aGNRs.

(Invited) Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a new class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7,5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions additional, gate-dependent emission lines appear which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6,5) nanotubes. We also compare functionalized (7,5) electroluminescence data with photoluminescence of pristine and functionalized (7,5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.Reference: Min-Ken Li et al., ACS Nano 2022 (doi: 10.1021/acsnano.2c03083) Figure 1