As the anode material of LIBs, the SnS2 electrode boasts a reversible specific capacity as high as 1231 mAh g-1. Additionally, SnS2 possesses a CdI2-type layered structure with a layer spacing of 0.59 nm, which allows it to accommodate numerous lithium ions and facilitate rapid charge transfer. However, as a semiconductor material, SnS2's low electronic conductivity significantly hampers its the lithium storage performance. In this paper, we propose enhancing intrinsic electronic conductance of SnS2 through fluorine doping and the introducing of sulfur vacancies, thereby constructing the F-SnS2-x structure. The stability and superiority of this structure are confirmed by a series of theoretical calculations. The stability and rationality of the structure were characterized by phonon spectrum. Calculation of the density of state and lithium ion diffusion barrier demonstrate that F-SnS2-x has exhibits exceptional electron/lithium ion transport kinetics. Furthermore, the results of lithium ion binding energy and differential charge show that there is a strong interaction between F-SnS2-x structure and lithium ion, which is advantageous for achieving long-term cycle stability. Importantly, one F-SnS2-x molecule can adsorb up to 4.5 Li atom, yielding a corresponding theoretical specific capacity of 702 mAh g-1, which surpasses that of SnS2 with 4 atoms (586 mAh g-1). The theoretical calculation results of this work can provide valuable insights for improving the electronic conductivity and lithium storage performance of other metal sulfides.
{"title":"Effect of introducing fluorine doping and sulfur vacancy on SnS2 as anode electrode of LIBs: a density functional theory","authors":"Jiayi Guan, Kaihui Lin, Yanbing Liao, Zhiling Xu, Yuda Lin, Shenghui Zheng","doi":"10.1039/d4cp04032e","DOIUrl":"https://doi.org/10.1039/d4cp04032e","url":null,"abstract":"As the anode material of LIBs, the SnS2 electrode boasts a reversible specific capacity as high as 1231 mAh g-1. Additionally, SnS2 possesses a CdI2-type layered structure with a layer spacing of 0.59 nm, which allows it to accommodate numerous lithium ions and facilitate rapid charge transfer. However, as a semiconductor material, SnS2's low electronic conductivity significantly hampers its the lithium storage performance. In this paper, we propose enhancing intrinsic electronic conductance of SnS2 through fluorine doping and the introducing of sulfur vacancies, thereby constructing the F-SnS2-x structure. The stability and superiority of this structure are confirmed by a series of theoretical calculations. The stability and rationality of the structure were characterized by phonon spectrum. Calculation of the density of state and lithium ion diffusion barrier demonstrate that F-SnS2-x has exhibits exceptional electron/lithium ion transport kinetics. Furthermore, the results of lithium ion binding energy and differential charge show that there is a strong interaction between F-SnS2-x structure and lithium ion, which is advantageous for achieving long-term cycle stability. Importantly, one F-SnS2-x molecule can adsorb up to 4.5 Li atom, yielding a corresponding theoretical specific capacity of 702 mAh g-1, which surpasses that of SnS2 with 4 atoms (586 mAh g-1). The theoretical calculation results of this work can provide valuable insights for improving the electronic conductivity and lithium storage performance of other metal sulfides.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pierre L Stigliano, Antonela Gallastegui, Thomas H Smith, Luke Austin O'Dell, David Mecerreyes, Cristina Pozo-Gonzalo, Maria Forsyth
In this work, we investigate the development of polymer electrolytes for sodium batteries based on sulfonamide functional polymer nanoparticles (NaNPs). The synthesis of the polymer NaNPs is carried out by emulsion copolymerization of methyl methacrylate and sodium sulfonamide methacrylate in the presence of a crosslinker, resulting in particle sizes of 50 nm, as shown by electron microscopy. Then, gel polymer electrolytes are prepared by mixing polymer NPs and different organic plasticizers including carbonates, glymes, sulfolane and ionic liquids. The chemical nature of the plasticizer resulted in different effects on the sodium coordination shell, which in turn impacted the properties of each membrane as investigated by FTIR. The transport properties were investigated by EIS and solid-state NMR. Among the organic gel polymer electrolytes (GPEs), the system comprising NaNPs and sulfolane achieved the best ionic conductivity (1.1 x 10-4 S cm-1 at 50 °C) and sodium single-ion properties while for the ionogels, the best ionic conductivity was obtained by NaNPs mixed with pyrrolidinium-FSI IL (4.7 x 10-4 S cm-1 at 50 °C). From sodium metal symmetrical cells cycling, the use of ILs as plasticizers proved to be more beneficial for SEI formation and its evolution during cell cycling compared to the systems based on NPs and organic solvents. However, NPs+PC led to lower cell overvoltage than NPs+ILs (<0.4 V vs >0.5 V). This study shows the potential of using Na-sulfonamide functional polymer nanoparticles to immobilize different plasticizers and thereby obtain soft-solid electrolytes for Na metal batteries.
{"title":"Gel Polymer Electrolytes Based on Sulfonamide Functional Polymer Nanoparticles for Sodium Metal Batteries","authors":"Pierre L Stigliano, Antonela Gallastegui, Thomas H Smith, Luke Austin O'Dell, David Mecerreyes, Cristina Pozo-Gonzalo, Maria Forsyth","doi":"10.1039/d4cp04703f","DOIUrl":"https://doi.org/10.1039/d4cp04703f","url":null,"abstract":"In this work, we investigate the development of polymer electrolytes for sodium batteries based on sulfonamide functional polymer nanoparticles (NaNPs). The synthesis of the polymer NaNPs is carried out by emulsion copolymerization of methyl methacrylate and sodium sulfonamide methacrylate in the presence of a crosslinker, resulting in particle sizes of 50 nm, as shown by electron microscopy. Then, gel polymer electrolytes are prepared by mixing polymer NPs and different organic plasticizers including carbonates, glymes, sulfolane and ionic liquids. The chemical nature of the plasticizer resulted in different effects on the sodium coordination shell, which in turn impacted the properties of each membrane as investigated by FTIR. The transport properties were investigated by EIS and solid-state NMR. Among the organic gel polymer electrolytes (GPEs), the system comprising NaNPs and sulfolane achieved the best ionic conductivity (1.1 x 10<small><sup>-4</sup></small> S cm<small><sup>-1</sup></small> at 50 °C) and sodium single-ion properties while for the ionogels, the best ionic conductivity was obtained by NaNPs mixed with pyrrolidinium-FSI IL (4.7 x 10<small><sup>-4</sup></small> S cm<small><sup>-1</sup></small> at 50 °C). From sodium metal symmetrical cells cycling, the use of ILs as plasticizers proved to be more beneficial for SEI formation and its evolution during cell cycling compared to the systems based on NPs and organic solvents. However, NPs+PC led to lower cell overvoltage than NPs+ILs (<0.4 V vs >0.5 V). This study shows the potential of using Na-sulfonamide functional polymer nanoparticles to immobilize different plasticizers and thereby obtain soft-solid electrolytes for Na metal batteries.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hicham Idriss, María Andrea Barral, Solange Mariel Di Napoli, Verónica Laura Vildosola, Christof Wöll, Veronica Ganduglia-Pirovano, Ana Maria LIois, Eric Sauter, Gustavo E. Murgida
Within the framework of surface-adsorbate interactions relevant to chemical reactions of spent nuclear fuel, the study of actinide oxide systems remains one of the most challenging tasks at both the experimental and computational levels. Consequently, our understanding of the effect of their unique electronic configurations on surface reactions lags behind that of d-block oxides. To investigate the surface properties of this system, we present the first infrared spectroscopy analysis of carbon monoxide (CO) interaction with a monocrystalline actinide oxide, UO₂(111). Using a monocrystalline form avoids issues related to super-stoichiometries (UO2+x) and makes the experimental data suitable for further theoretical studies. Our findings reveal that CO adsorbs molecularly and shows a pronounced blue shift of the vibrational frequency to 2160 cm⁻¹ relative to the gas-phase value. Interpreted through Density Functional Theory (DFT) at different levels of computation, results indicate that to accurately describe the interaction between the CO molecule and the surface, it is essential to consider hybrid functionals, the non-collinearity of uranium's local magnetic moments, and spin-orbit coupling. Moreover, an intense IR absorption band at 978 cm⁻¹ emerged upon CO exposure, tentatively attributed to the O-U-O asymmetric stretch of surface substrate vibration. This new band, together with the observation of the importance of the relativistic effect in determining the nature of the chemical bonding of CO, is poised to broaden our understanding of actinide surface reactions.
{"title":"Exploring Molecule-Surface Interactions of Urania via IR Spectroscopy and Density Functional Theory.","authors":"Hicham Idriss, María Andrea Barral, Solange Mariel Di Napoli, Verónica Laura Vildosola, Christof Wöll, Veronica Ganduglia-Pirovano, Ana Maria LIois, Eric Sauter, Gustavo E. Murgida","doi":"10.1039/d4cp03096f","DOIUrl":"https://doi.org/10.1039/d4cp03096f","url":null,"abstract":"Within the framework of surface-adsorbate interactions relevant to chemical reactions of spent nuclear fuel, the study of actinide oxide systems remains one of the most challenging tasks at both the experimental and computational levels. Consequently, our understanding of the effect of their unique electronic configurations on surface reactions lags behind that of d-block oxides. To investigate the surface properties of this system, we present the first infrared spectroscopy analysis of carbon monoxide (CO) interaction with a monocrystalline actinide oxide, UO₂(111). Using a monocrystalline form avoids issues related to super-stoichiometries (UO2+x) and makes the experimental data suitable for further theoretical studies. Our findings reveal that CO adsorbs molecularly and shows a pronounced blue shift of the vibrational frequency to 2160 cm⁻¹ relative to the gas-phase value. Interpreted through Density Functional Theory (DFT) at different levels of computation, results indicate that to accurately describe the interaction between the CO molecule and the surface, it is essential to consider hybrid functionals, the non-collinearity of uranium's local magnetic moments, and spin-orbit coupling. Moreover, an intense IR absorption band at 978 cm⁻¹ emerged upon CO exposure, tentatively attributed to the O-U-O asymmetric stretch of surface substrate vibration. This new band, together with the observation of the importance of the relativistic effect in determining the nature of the chemical bonding of CO, is poised to broaden our understanding of actinide surface reactions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Graphitic carbon nitride (g-C3N4) is a useful photocatalyst applied in various areas. However, it has some disadvantages that limit its applications. Therefore, doping and the construction of heterojunction are beneficial methods to overcome these drawbacks. ZnS is one of the photocatalysts that can be combined with g-C3N4. The sulfur vacancy defect in ZnS enhances its ability to adsorb visible light compared to bare ZnS. In this work, we theoretically investigated bulk g-C3N4 (g-C3N4-B), monolayer g-C3N4 (g-C3N4-M), ZnS, and defective ZnS (ZnS-D) using the SIESTA package. Subsequently, the position of conduction band minimum (CBM) and valance band maximum (VB) of g-C3N4-B and g-C3N4-M were plotted relative to the CBM and VBM of ZnS-B and ZnS-D. The results showed that g-C3N4/ZnS heterojunction is more suitable than g-C3N4/ZnS-D. This heterojunction is a Z-scheme type, which increases the lifetime of carriers. On the other hand, it is a narrow gap semiconductor that can be used in thermoelectric devices, the amount of Seebeck coefficients confirms that the heterojunction enhances the thermoelectric properties of photocatalysts. Our results demonstrate that the Z-scheme mechanism enhances the lifetime of carriers and thermoelectric properties.
{"title":"The theoretical investigation of g-C3N4/ZnS heterojunction for photocatalytic applications","authors":"Elnaz Ranjbakhsh, Mohammad Izadyar","doi":"10.1039/d3cp04372j","DOIUrl":"https://doi.org/10.1039/d3cp04372j","url":null,"abstract":"Graphitic carbon nitride (g-C3N4) is a useful photocatalyst applied in various areas. However, it has some disadvantages that limit its applications. Therefore, doping and the construction of heterojunction are beneficial methods to overcome these drawbacks. ZnS is one of the photocatalysts that can be combined with g-C3N4. The sulfur vacancy defect in ZnS enhances its ability to adsorb visible light compared to bare ZnS. In this work, we theoretically investigated bulk g-C3N4 (g-C3N4-B), monolayer g-C3N4 (g-C3N4-M), ZnS, and defective ZnS (ZnS-D) using the SIESTA package. Subsequently, the position of conduction band minimum (CBM) and valance band maximum (VB) of g-C3N4-B and g-C3N4-M were plotted relative to the CBM and VBM of ZnS-B and ZnS-D. The results showed that g-C3N4/ZnS heterojunction is more suitable than g-C3N4/ZnS-D. This heterojunction is a Z-scheme type, which increases the lifetime of carriers. On the other hand, it is a narrow gap semiconductor that can be used in thermoelectric devices, the amount of Seebeck coefficients confirms that the heterojunction enhances the thermoelectric properties of photocatalysts. Our results demonstrate that the Z-scheme mechanism enhances the lifetime of carriers and thermoelectric properties.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Morgan Larder, Jackson Crowley, Sheikh I. Hossain, Evelyne Deplazes
Steroids are organic compounds found in all forms of biological life. Besides their structural roles in cell membranes, steroids act as signalling molecules in various physiological processes and are used to treat inflammatory conditions. It has been hypothesised that in addition to their well-characterised genomic and non-genomic pathways, steroids exert their biological or pharmacological activities via an indirect, nonreceptor-mediated membrane mechanism caused by steroid-induced changes to the physicochemical properties of cell membranes. While the effect of cholesterol on phospholipid bilayer properties has been extensively studied, much less is known about the effect of other steroids and steroid-like molecules. Here, we combine electrical impedance spectroscopy (EIS) experiments with molecular dynamics (MD) simulations to study the effect of the steroids cortisone, prednisolone and progesterone and the steroid-like compounds enoxolone and carbenoxolone on the ion permeability and structure of phospholipid bilayers composed of the zwitterionic lipid POPC. The EIS data shows that all five compounds increase permeability, while the simulations suggest that this is accompanied by a thinning of the bilayer and reduced lipid order. We show that for steroids, a previously proposed structure–activity relationship that classifies steroids into order-promoting or order-disrupting compounds based on domain formations translates to ion permeability. We confirmed this by additional experiments with cholesterol and 7-ketocholesterol. In contrast, the previously reported relationship between log P and molecular area and a steroid being a promoter does not translate to the steroid-like compounds enoxolone and carbenoxolone. We propose that their membrane-disruption activity can be explained by their hydrogen-bonding capacity that dictates the compound's orientation at the water–lipid interface. Specifically, their membrane-disrupting ability is a result of the steroids to intercalate between lipids and form stable interactions with lipid headgroups and interfacial water, thereby pushing lipids apart and lowering the energy required for ion-induced pores, an effect previously reported for other membrane-altering small molecules.
{"title":"Steroids and steroid-like compounds alter the ion permeability of phospholipid bilayers via distinct interactions with lipids and interfacial water","authors":"Morgan Larder, Jackson Crowley, Sheikh I. Hossain, Evelyne Deplazes","doi":"10.1039/d4cp03254c","DOIUrl":"https://doi.org/10.1039/d4cp03254c","url":null,"abstract":"Steroids are organic compounds found in all forms of biological life. Besides their structural roles in cell membranes, steroids act as signalling molecules in various physiological processes and are used to treat inflammatory conditions. It has been hypothesised that in addition to their well-characterised genomic and non-genomic pathways, steroids exert their biological or pharmacological activities <em>via</em> an indirect, nonreceptor-mediated membrane mechanism caused by steroid-induced changes to the physicochemical properties of cell membranes. While the effect of cholesterol on phospholipid bilayer properties has been extensively studied, much less is known about the effect of other steroids and steroid-like molecules. Here, we combine electrical impedance spectroscopy (EIS) experiments with molecular dynamics (MD) simulations to study the effect of the steroids cortisone, prednisolone and progesterone and the steroid-like compounds enoxolone and carbenoxolone on the ion permeability and structure of phospholipid bilayers composed of the zwitterionic lipid POPC. The EIS data shows that all five compounds increase permeability, while the simulations suggest that this is accompanied by a thinning of the bilayer and reduced lipid order. We show that for steroids, a previously proposed structure–activity relationship that classifies steroids into order-promoting or order-disrupting compounds based on domain formations translates to ion permeability. We confirmed this by additional experiments with cholesterol and 7-ketocholesterol. In contrast, the previously reported relationship between log <em>P</em> and molecular area and a steroid being a promoter does not translate to the steroid-like compounds enoxolone and carbenoxolone. We propose that their membrane-disruption activity can be explained by their hydrogen-bonding capacity that dictates the compound's orientation at the water–lipid interface. Specifically, their membrane-disrupting ability is a result of the steroids to intercalate between lipids and form stable interactions with lipid headgroups and interfacial water, thereby pushing lipids apart and lowering the energy required for ion-induced pores, an effect previously reported for other membrane-altering small molecules.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The ground and excited state electronic structure of the molecular photoswitches quadricyclane and norbornadiene is examined qualitatively and quantitatively. A new custom basis set is introduced, optimised for efficient yet accurate calculations. A number of advanced multi-configurational and multi-reference electronic structure methods are evaluated, identifying those sufficiently accurate and efficient to be used in on-the-fly simulations of photoexcited dynamics. The key valence states participating in the isomerisation reaction are investigated, specifically mapping the important S1/S0 conical intersection that governs the non-radiative decay of the excited system. The powerful yet simple three-state valence model introduced here provides a suitable base for future computational exploration of the photodynamics of the substituted molecules suitable for e.g. energy-storage applications.
{"title":"Electronic structure of norbornadiene and quadricyclane","authors":"Joseph C. Cooper, Adam Kirrander","doi":"10.1039/d4cp03960b","DOIUrl":"https://doi.org/10.1039/d4cp03960b","url":null,"abstract":"The ground and excited state electronic structure of the molecular photoswitches quadricyclane and norbornadiene is examined qualitatively and quantitatively. A new custom basis set is introduced, optimised for efficient yet accurate calculations. A number of advanced multi-configurational and multi-reference electronic structure methods are evaluated, identifying those sufficiently accurate and efficient to be used in on-the-fly simulations of photoexcited dynamics. The key valence states participating in the isomerisation reaction are investigated, specifically mapping the important S1/S0 conical intersection that governs the non-radiative decay of the excited system. The powerful yet simple three-state valence model introduced here provides a suitable base for future computational exploration of the photodynamics of the substituted molecules suitable for e.g. energy-storage applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Exploring valleytronics in two-dimensional materials is of great significance for the development of advanced information devices. In this study, we investigate the valley polarization and electronic properties of V-doped 2H-phase Janus MoSeTe by using first-principles calculations. Our results reveal a remarkable valley spin splitting up to 60 meV, driven by the breaking of time-reversal symmetry due to the magnetic effect of the V 3d orbitals. Additionally, we observe the anomalous valley Hall effect (AVHE) in V-doped 2-H phase Janus MoSeTe monolayer, showcasing its potential for valleytronic applications. Importantly, we found that the valley polarization can be effectively modulated by applying external strain, with notable changes at different strain levels. These findings suggest that monolayer V-doped 2H-phase Janus MoSeTe is an ideal material to design of tunable, controllable valleytronic devices, offering new opportunities for the next generation of vally-based technologies.
{"title":"Enhancing Valley Splitting and Anomalous Valley Hall Effect in V-Doped Janus MoSeTe monolayer","authors":"Shulai Lei, jiayao wang, Rongli Zhao, Jinbo Sun, Shujuan Li, Xinyue Xiong, Yin Wang, Ke Xu","doi":"10.1039/d4cp04412f","DOIUrl":"https://doi.org/10.1039/d4cp04412f","url":null,"abstract":"Exploring valleytronics in two-dimensional materials is of great significance for the development of advanced information devices. In this study, we investigate the valley polarization and electronic properties of V-doped 2H-phase Janus MoSeTe by using first-principles calculations. Our results reveal a remarkable valley spin splitting up to 60 meV, driven by the breaking of time-reversal symmetry due to the magnetic effect of the V 3d orbitals. Additionally, we observe the anomalous valley Hall effect (AVHE) in V-doped 2-H phase Janus MoSeTe monolayer, showcasing its potential for valleytronic applications. Importantly, we found that the valley polarization can be effectively modulated by applying external strain, with notable changes at different strain levels. These findings suggest that monolayer V-doped 2H-phase Janus MoSeTe is an ideal material to design of tunable, controllable valleytronic devices, offering new opportunities for the next generation of vally-based technologies.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jasleen K. Bindra, Jens Niklas, Yeonjun Jeong, Ahren Jasper, Lisa Marie Utschig, Oleg Poluektov
Photosynthetic reaction center proteins (RCs) provide ideal model systems for studying quantum entanglement between multiple spins, a quantum mechanical phenomenon wherein the properties of the entangled particles become inherently correlated. Following light-generated sequential electron transfer, RCs generate spin-correlated radical pairs (SCRPs), also referred to as entangled spin qubit (radical) pairs (SQP). Understanding and controlling coherence mechanisms in SCRP/SQPs is important for realizing practical uses of electron spin qubits in quantum sensing applications. The bacterial RC (bRCs) provides an experimental system for exploring quantum effects in the SCRP P865+QA-, where P865, a special pair of bacteriochlorophylls, is the primary donor, and QA is the primary quinone acceptor. In this study, we focus on understanding how local molecular environments and isotopic substitution, particularly deuteration, influence spin coherence times (TM). Using high-frequency electron paramagnetic resonance (EPR) spectroscopy, we observed that the local environment surrounding P865 and QA plays a significant role in determining TM. Our findings show that while deuteration led to a modest increase in TM, particularly at low temperatures, the effect was substantially smaller in Zn-substituted bRCs than predicted by classical nuclear spin diffusion alone. This result is in contrast to our previous study of the photosystem I (PSI) RC, where no increase in TM was measured upon deuteration. Theoretical modeling identified several methyl groups at key distances from the spin centers of both bRC and PSI, and methyl group tunneling at low temperatures has been previously suggested as a mechanism for enhanced spin decoherence. Additionally, our study revealed a strong dependence of spin coherence on the orientation of the external magnetic field, highlighting the influence of the protein microenvironment on spin dynamics. These results offer new insights for optimizing coherence times in quantum system design for quantum information science and sensing applications.
{"title":"Light-Induced Electron Spin Qubit Coherences in the Purple Bacterial Reaction Center Protein","authors":"Jasleen K. Bindra, Jens Niklas, Yeonjun Jeong, Ahren Jasper, Lisa Marie Utschig, Oleg Poluektov","doi":"10.1039/d4cp03971h","DOIUrl":"https://doi.org/10.1039/d4cp03971h","url":null,"abstract":"Photosynthetic reaction center proteins (RCs) provide ideal model systems for studying quantum entanglement between multiple spins, a quantum mechanical phenomenon wherein the properties of the entangled particles become inherently correlated. Following light-generated sequential electron transfer, RCs generate spin-correlated radical pairs (SCRPs), also referred to as entangled spin qubit (radical) pairs (SQP). Understanding and controlling coherence mechanisms in SCRP/SQPs is important for realizing practical uses of electron spin qubits in quantum sensing applications. The bacterial RC (bRCs) provides an experimental system for exploring quantum effects in the SCRP P865+QA-, where P865, a special pair of bacteriochlorophylls, is the primary donor, and QA is the primary quinone acceptor. In this study, we focus on understanding how local molecular environments and isotopic substitution, particularly deuteration, influence spin coherence times (TM). Using high-frequency electron paramagnetic resonance (EPR) spectroscopy, we observed that the local environment surrounding P865 and QA plays a significant role in determining TM. Our findings show that while deuteration led to a modest increase in TM, particularly at low temperatures, the effect was substantially smaller in Zn-substituted bRCs than predicted by classical nuclear spin diffusion alone. This result is in contrast to our previous study of the photosystem I (PSI) RC, where no increase in TM was measured upon deuteration. Theoretical modeling identified several methyl groups at key distances from the spin centers of both bRC and PSI, and methyl group tunneling at low temperatures has been previously suggested as a mechanism for enhanced spin decoherence. Additionally, our study revealed a strong dependence of spin coherence on the orientation of the external magnetic field, highlighting the influence of the protein microenvironment on spin dynamics. These results offer new insights for optimizing coherence times in quantum system design for quantum information science and sensing applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ni2Mn1+xZ1−x (Z = In, Sn or Sb) undergo martensitic transformation with transformation temperature (TM) scaling with the average valence electron per atom (e/a) ratio. However, the rate of increase of TM depends on the type of Z atom, with the slope of TM vs e/a curve increasing from Z = Into Z = Sb. Local structural distortions are believed to be the leading cause of martensitic transformation in these alloys. A careful study of the Ni and Mn local structures in several Ni2Mn1+xZ1−x alloys with varying e/a ratio and the same Z atom, with the same e/a ratio but different Z atoms and with the same TM but with different Z atoms and different e/a ratio, revealed that the difference between Ni-Mn and Ni-Z nearest neighbor distances decreases as the Z atom changes from In to Sb. This decrease in the local structural distortion accommodates a higher content of Mn until the L21 structure becomes unstable and the alloy undergoes a martensitic transformation.
{"title":"Role of local structural distortions in the variation of martensitic transformation temperature with e/a ratio in Ni2Mn1+xZ1−x (Z = In, Sn or Sb) alloys","authors":"Nafea Manea, Edmund Welter, Kaustubh Priolkar","doi":"10.1039/d4cp04014g","DOIUrl":"https://doi.org/10.1039/d4cp04014g","url":null,"abstract":"Ni<small><sub>2</sub></small>Mn<small><sub>1+x</sub></small>Z<small><sub>1−x</sub></small> (Z = In, Sn or Sb) undergo martensitic transformation with transformation temperature (T<small><sub>M</sub></small>) scaling with the average valence electron per atom (e/a) ratio. However, the rate of increase of T<small><sub>M</sub></small> depends on the type of Z atom, with the slope of T<small><sub>M</sub></small> vs e/a curve increasing from Z = Into Z = Sb. Local structural distortions are believed to be the leading cause of martensitic transformation in these alloys. A careful study of the Ni and Mn local structures in several Ni<small><sub>2</sub></small>Mn<small><sub>1+x</sub></small>Z<small><sub>1−x</sub></small> alloys with varying e/a ratio and the same Z atom, with the same e/a ratio but different Z atoms and with the same T<small><sub>M</sub></small> but with different Z atoms and different e/a ratio, revealed that the difference between Ni-Mn and Ni-Z nearest neighbor distances decreases as the Z atom changes from In to Sb. This decrease in the local structural distortion accommodates a higher content of Mn until the L2<small><sub>1</sub></small> structure becomes unstable and the alloy undergoes a martensitic transformation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"133 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935136","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study employs first-principles calculations to investigate the geometric and electronic properties of hydrogenated silicon nanotubes (SiNTs). SiNTs, particularly in their gear-like configuration, demonstrate unique semiconducting behavior; however, their relatively small intrinsic band gaps limit their applicability in fields requiring moderate band gaps. Significant changes in electronic properties are observed by hydrogenating SiNTs at various levels of adsorption—either full or partial—and different surface configurations (exterior, interior, or dual-sided). These changes include band gap tuning, metal–semiconductor transitions, and enhanced material stability. Generally, complete hydrogen adsorption increases the band gap, while partial hydrogen adsorption can induce metallic or half-metallic characteristics. The study also highlights the significance of spatial charge density redistribution in determining the electronic behavior of SiNTs under hydrogen doping, underscoring their potential for use in electronics, sensors, and energy storage applications.
{"title":"Modulating electronic properties in hydrogenated silicon nanotubes","authors":"Hsin-Yi Liu, Jhao-Ying Wu","doi":"10.1039/d4cp03703k","DOIUrl":"https://doi.org/10.1039/d4cp03703k","url":null,"abstract":"This study employs first-principles calculations to investigate the geometric and electronic properties of hydrogenated silicon nanotubes (SiNTs). SiNTs, particularly in their gear-like configuration, demonstrate unique semiconducting behavior; however, their relatively small intrinsic band gaps limit their applicability in fields requiring moderate band gaps. Significant changes in electronic properties are observed by hydrogenating SiNTs at various levels of adsorption—either full or partial—and different surface configurations (exterior, interior, or dual-sided). These changes include band gap tuning, metal–semiconductor transitions, and enhanced material stability. Generally, complete hydrogen adsorption increases the band gap, while partial hydrogen adsorption can induce metallic or half-metallic characteristics. The study also highlights the significance of spatial charge density redistribution in determining the electronic behavior of SiNTs under hydrogen doping, underscoring their potential for use in electronics, sensors, and energy storage applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"56 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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