Correction for 'Electrolyte clusters as hydrogen sponges: diffusion Monte Carlo simulations' by A. R. Zane et al., Phys. Chem. Chem. Phys., 2022, 24, 26094-26101, https://doi.org/10.1039/D2CP03658D.
{"title":"Correction: Electrolyte clusters as hydrogen sponges: diffusion Monte Carlo simulations.","authors":"A R Zane, E Curotto","doi":"10.1039/d5cp90227d","DOIUrl":"https://doi.org/10.1039/d5cp90227d","url":null,"abstract":"<p><p>Correction for 'Electrolyte clusters as hydrogen sponges: diffusion Monte Carlo simulations' by A. R. Zane <i>et al.</i>, <i>Phys. Chem. Chem. Phys.</i>, 2022, <b>24</b>, 26094-26101, https://doi.org/10.1039/D2CP03658D.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145712653","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}
Lithium-rich manganese-based cathode materials have attracted significant attention due to their high capacity potential and the involvement of oxygen anions in redox reactions. However, their practical application is severely limited by the persistent voltage hysteresis observed during charge-discharge cycles. To uncover the fundamental mechanism behind this phenomenon, this study employs first-principles calculations based on density functional theory to systematically investigate the thermodynamic stability and kinetic behavior of lithium migration during the delithiation-lithiation process. In a novel approach, the redox reaction is decoupled into two distinct stages: lithium-ion migration and electron transfer. Electron-deficient and electron-enriched models were constructed to simulate the electrochemical directionality of charging and discharging, and the migration pathways and energy barriers of lithium ions in different configurations were calculated. Combined with Bader charge analysis and density of states calculations, the results reveal that lithium ions preferentially migrate from the transition metal layer, exhibiting a clear “first-in-first-out” kinetic behavior. This asymmetric migration leads to mismatched charge-discharge pathways, which is identified as the root cause of voltage hysteresis. These findings provide atomic-scale insight into the origin of voltage hysteresis, offer a new theoretical perspective on the nonequilibrium structural evolution of lithium-rich materials, and lay a solid foundation for the rational design of next generation high energy density cathode materials with improved electrochemical performance.
{"title":"First-Principles Investigation of Lithium Ion First-In-First-Out Behavior during Delithiation and Lithiation Processes in Li2MnO3 Lithium-Rich Cathode Material","authors":"Yuyang Chen, Yuxin Wei, Yunsong Zhang, Rui Li","doi":"10.1039/d5cp01998b","DOIUrl":"https://doi.org/10.1039/d5cp01998b","url":null,"abstract":"Lithium-rich manganese-based cathode materials have attracted significant attention due to their high capacity potential and the involvement of oxygen anions in redox reactions. However, their practical application is severely limited by the persistent voltage hysteresis observed during charge-discharge cycles. To uncover the fundamental mechanism behind this phenomenon, this study employs first-principles calculations based on density functional theory to systematically investigate the thermodynamic stability and kinetic behavior of lithium migration during the delithiation-lithiation process. In a novel approach, the redox reaction is decoupled into two distinct stages: lithium-ion migration and electron transfer. Electron-deficient and electron-enriched models were constructed to simulate the electrochemical directionality of charging and discharging, and the migration pathways and energy barriers of lithium ions in different configurations were calculated. Combined with Bader charge analysis and density of states calculations, the results reveal that lithium ions preferentially migrate from the transition metal layer, exhibiting a clear “first-in-first-out” kinetic behavior. This asymmetric migration leads to mismatched charge-discharge pathways, which is identified as the root cause of voltage hysteresis. These findings provide atomic-scale insight into the origin of voltage hysteresis, offer a new theoretical perspective on the nonequilibrium structural evolution of lithium-rich materials, and lay a solid foundation for the rational design of next generation high energy density cathode materials with improved electrochemical performance.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"93 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753209","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}
Wojciech Petrykowski, Marzena Banasiewicz, Olaf Morawski, Zbigniew Kaluza, Cristina Aparecida Barboza, Daniel T. Gryko
The photophysics of two series of 1,4-dihydro-tetraaryl-pyrrolo[3,2-b]pyrroles possessing N-aryl substituents of various electronic character was investigated systematically. The molecular structure of these compounds was designed so that their solubility enabled us to study absorption and emission in a broad range of solvents. The presence of N-4-nitrophenyl substituents is responsible for charge-transfer absorption band and shifts the emission band hypsochromically. At the same time, their presence quenches fluorescence, although if electron-withdrawing substituents are present at positions 2 and 5, this effect is reduced by an order of magnitude. In the case of less electron-withdrawing N-4-cyanophenyl and N-3-cyanophenyl groups strong emission is present only if the electron-withdrawing groups are located at positions 2 and 5. The combined experimental and computational study point out the existence of a barrier between au (bright) and ag (dark) CT states, the height of which is the key factor governing the fate of these molecules in the excited state. Weaker electronic communication at positions 1 and 4 of DHPP core is responsible for strong charge separation. Polar solvents favor the formation of transient dipole moments due to excited-state symmetry-breaking, which amplifies the nonradiative deactivation of nitro-TAPPs. Conversely, moderate to weak electron-donating groups favor strong LE emission.
{"title":"N-Aryl substituents have the influence on photophysics of tetraaryl-pyrrolo[3,2-b]pyrroles","authors":"Wojciech Petrykowski, Marzena Banasiewicz, Olaf Morawski, Zbigniew Kaluza, Cristina Aparecida Barboza, Daniel T. Gryko","doi":"10.1039/d5cp03474d","DOIUrl":"https://doi.org/10.1039/d5cp03474d","url":null,"abstract":"The photophysics of two series of 1,4-dihydro-tetraaryl-pyrrolo[3,2-b]pyrroles possessing N-aryl substituents of various electronic character was investigated systematically. The molecular structure of these compounds was designed so that their solubility enabled us to study absorption and emission in a broad range of solvents. The presence of N-4-nitrophenyl substituents is responsible for charge-transfer absorption band and shifts the emission band hypsochromically. At the same time, their presence quenches fluorescence, although if electron-withdrawing substituents are present at positions 2 and 5, this effect is reduced by an order of magnitude. In the case of less electron-withdrawing N-4-cyanophenyl and N-3-cyanophenyl groups strong emission is present only if the electron-withdrawing groups are located at positions 2 and 5. The combined experimental and computational study point out the existence of a barrier between au (bright) and ag (dark) CT states, the height of which is the key factor governing the fate of these molecules in the excited state. Weaker electronic communication at positions 1 and 4 of DHPP core is responsible for strong charge separation. Polar solvents favor the formation of transient dipole moments due to excited-state symmetry-breaking, which amplifies the nonradiative deactivation of nitro-TAPPs. Conversely, moderate to weak electron-donating groups favor strong LE emission.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728757","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}
Li-Ting Yuan,Chen-Yu Hu,Ji-Yong Yang,Gang Yao,Ming-Long Tao,Kai Sun,Jun-Zhong Wang
We report a scanning tunnelling microscopy (STM) study on the collective chirality flipping of dibenzopentacene (DBPen) molecules on Cd(0001). It is observed that the DBPen monolayer formed on Cd(0001) is composed of parallel molecular rows, which exhibit two enantiomeric lattices (chiral domains). The flat-lying molecules in the parallel rows exhibit an S-like shape with clockwise or anticlockwise handedness (single-molecule chirality). In particular, the pulse voltages from the STM tip lead to the simultaneous rotations of molecular rows and long-molecular-axes. When the two rotations have the same angle, pure lattice rotation takes place in the DBPen monolayer. When the two rotational angles are different, collective chirality flipping takes place in the homochiral domains, accompanied by the reversal of lattice chirality. Statistical analysis demonstrates that the chirality flipping takes place only at large negative pulse voltage, and there is a weak dependence of the chiral reversal probability on the tunnelling current, suggesting that the electric field of the STM tip is the primary driving force for chirality reversal.
{"title":"Collective chirality flipping of dibenzopentacene molecules induced by an electric field.","authors":"Li-Ting Yuan,Chen-Yu Hu,Ji-Yong Yang,Gang Yao,Ming-Long Tao,Kai Sun,Jun-Zhong Wang","doi":"10.1039/d5cp03453a","DOIUrl":"https://doi.org/10.1039/d5cp03453a","url":null,"abstract":"We report a scanning tunnelling microscopy (STM) study on the collective chirality flipping of dibenzopentacene (DBPen) molecules on Cd(0001). It is observed that the DBPen monolayer formed on Cd(0001) is composed of parallel molecular rows, which exhibit two enantiomeric lattices (chiral domains). The flat-lying molecules in the parallel rows exhibit an S-like shape with clockwise or anticlockwise handedness (single-molecule chirality). In particular, the pulse voltages from the STM tip lead to the simultaneous rotations of molecular rows and long-molecular-axes. When the two rotations have the same angle, pure lattice rotation takes place in the DBPen monolayer. When the two rotational angles are different, collective chirality flipping takes place in the homochiral domains, accompanied by the reversal of lattice chirality. Statistical analysis demonstrates that the chirality flipping takes place only at large negative pulse voltage, and there is a weak dependence of the chiral reversal probability on the tunnelling current, suggesting that the electric field of the STM tip is the primary driving force for chirality reversal.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"35 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704469","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}
Timothy M E Jugovic,Henry E Thurber,Michael T Robo,Woojung Ji,Madeline E Clough,Anne J McNeil,Paul M Zimmerman
Adhesive-coated substrates have been used to non-selectively capture microplastics (MPs) in water. This work explores whether selective MP capture is plausible by modifying the adhesive structure. To find the degree of selectivity, adhesive strength might be estimated by examining surface interactions between specific adhesives and MPs. Herein, we describe the use of atomistic simulations to predict the aqueous adhesive strength via the aqueous work-of-adhesion (WoA(aq)), a thermodynamic measure of adhesion. Simulation of four common MPs and five different polyacrylate adhesives were conducted. The simulations show that fluorinated sidechains, due to their low interfacial energies and higher surface energies, exhibit increased selectivity toward polystyrene over other plastics. To provide experimental support for these predictions, probe-tack studies of aqueous adhesion were performed and found to agree with the simulations. Simulations also revealed non-intuitive interactions that govern WoA(aq), arising from the complex intra- and intermolecular interactions that occur when polyacrylates interface with water and MPs. This expanded understanding of the microscopic features of adhesion can be used to design next-generation adhesives and MP remediation technology.
{"title":"Predicting polyacrylate-microplastic interactions with atomistic simulation.","authors":"Timothy M E Jugovic,Henry E Thurber,Michael T Robo,Woojung Ji,Madeline E Clough,Anne J McNeil,Paul M Zimmerman","doi":"10.1039/d5cp03631c","DOIUrl":"https://doi.org/10.1039/d5cp03631c","url":null,"abstract":"Adhesive-coated substrates have been used to non-selectively capture microplastics (MPs) in water. This work explores whether selective MP capture is plausible by modifying the adhesive structure. To find the degree of selectivity, adhesive strength might be estimated by examining surface interactions between specific adhesives and MPs. Herein, we describe the use of atomistic simulations to predict the aqueous adhesive strength via the aqueous work-of-adhesion (WoA(aq)), a thermodynamic measure of adhesion. Simulation of four common MPs and five different polyacrylate adhesives were conducted. The simulations show that fluorinated sidechains, due to their low interfacial energies and higher surface energies, exhibit increased selectivity toward polystyrene over other plastics. To provide experimental support for these predictions, probe-tack studies of aqueous adhesion were performed and found to agree with the simulations. Simulations also revealed non-intuitive interactions that govern WoA(aq), arising from the complex intra- and intermolecular interactions that occur when polyacrylates interface with water and MPs. This expanded understanding of the microscopic features of adhesion can be used to design next-generation adhesives and MP remediation technology.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704441","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 discovery of selective and potent KRASG12D inhibitors remains a critical priority in oncology drug development. Here, we performed comparative all-atom molecular dynamics (MD) simulations on four KRASG12D–inhibitor complexes (PDB IDs: 7RPZ, 7RT2, 7EWB, 7EW9) spanning a wide affinity range (IC₅₀ = 2 nM–14 µM). Alchemical free-energy calculations yielded ΔG values of –11.3 to –6.2 kcal/mol, showing strong correlation with experimental pIC₅₀ (R² = 0.92). Per-residue energy decomposition identified three dominant polar interaction hotspots in high-affinity complexes (D12 ≈ –34 kcal/mol, E62 ≈ –20 kcal/mol, D69 ≈ –17 kcal/mol), whereas weak inhibitors showed markedly reduced contributions at these residues. Structural dynamics analysis revealed that strong binders maintained compact binding pockets (RMSD: 1.8–2.2 Å) with reduced ligand flexibility, while weak binders sampled expanded and unstable conformations (RMSD: 2.7–3.4 Å). These results quantitatively delineate the structural and energetic determinants governing KRASG12D inhibitor potency and provide data-driven guidelines for the design of next-generation KRASG12D inhibitors.
{"title":"Mechanistic Insights into KRAS G12D Inhibitor Binding Revealed by Molecular Dynamics Simulations of Multiple Crystal Structures†","authors":"donghwan kim, Eunho Lee, Sangbae Lee","doi":"10.1039/d5cp03384e","DOIUrl":"https://doi.org/10.1039/d5cp03384e","url":null,"abstract":"The discovery of selective and potent KRAS<small><sup>G12D</sup></small> inhibitors remains a critical priority in oncology drug development. Here, we performed comparative all-atom molecular dynamics (MD) simulations on four KRAS<small><sup>G12D</sup></small>–inhibitor complexes (PDB IDs: 7RPZ, 7RT2, 7EWB, 7EW9) spanning a wide affinity range (IC₅₀ = 2 nM–14 µM). Alchemical free-energy calculations yielded ΔG values of –11.3 to –6.2 kcal/mol, showing strong correlation with experimental pIC₅₀ (R² = 0.92). Per-residue energy decomposition identified three dominant polar interaction hotspots in high-affinity complexes (D12 ≈ –34 kcal/mol, E62 ≈ –20 kcal/mol, D69 ≈ –17 kcal/mol), whereas weak inhibitors showed markedly reduced contributions at these residues. Structural dynamics analysis revealed that strong binders maintained compact binding pockets (RMSD: 1.8–2.2 Å) with reduced ligand flexibility, while weak binders sampled expanded and unstable conformations (RMSD: 2.7–3.4 Å). These results quantitatively delineate the structural and energetic determinants governing KRAS<small><sup>G12D</sup></small> inhibitor potency and provide data-driven guidelines for the design of next-generation KRAS<small><sup>G12D</sup></small> inhibitors.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728700","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}
Composite pulses (CPs) are widely used in nuclear magnetic resonance (NMR), optical spectroscopy, optimal control experiments and quantum computing to manipulate systems that are well-described by a two-level Hamiltonian. A careful design of these pulses can allow the refocusing of an ensemble at a desired state, even if the ensemble experiences imperfections in the magnitude of the external field or resonance offsets. Since the introduction of CPs, several theoretical justifications for their robustness have been suggested. In this work, we suggest another justification based on the classical mechanical concept of a stability matrix. The motion on the Bloch sphere is mapped to a canonical system of coordinates and the focusing of an ensemble corresponds to caustics, or the vanishing of an appropriate stability matrix element in the canonical coordinates. Our approach highlights the directionality of the refocusing of the ensemble on the Bloch sphere, revealing how different ensembles refocus along different directions. The approach also clarifies when CPs can induce a change in the width of the ensemble as opposed to simply a rotation of the axes. As a case study, we investigate the 90(x)180(y)90(x) CP introduced by Levitt, where the approach provides a new perspective into why this CP is effective.
{"title":"The robustness of composite pulses elucidated by classical mechanics: stability around the globe","authors":"Jonathan Berkheim, David J. Tannor","doi":"10.1039/d5cp03162a","DOIUrl":"https://doi.org/10.1039/d5cp03162a","url":null,"abstract":"Composite pulses (CPs) are widely used in nuclear magnetic resonance (NMR), optical spectroscopy, optimal control experiments and quantum computing to manipulate systems that are well-described by a two-level Hamiltonian. A careful design of these pulses can allow the refocusing of an ensemble at a desired state, even if the ensemble experiences imperfections in the magnitude of the external field or resonance offsets. Since the introduction of CPs, several theoretical justifications for their robustness have been suggested. In this work, we suggest another justification based on the classical mechanical concept of a stability matrix. The motion on the Bloch sphere is mapped to a canonical system of coordinates and the focusing of an ensemble corresponds to caustics, or the vanishing of an appropriate stability matrix element in the canonical coordinates. Our approach highlights the directionality of the refocusing of the ensemble on the Bloch sphere, revealing how different ensembles refocus along different directions. The approach also clarifies when CPs can induce a change in the width of the ensemble as opposed to simply a rotation of the axes. As a case study, we investigate the 90(<em>x</em>)180(<em>y</em>)90(<em>x</em>) CP introduced by Levitt, where the approach provides a new perspective into why this CP is effective.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704797","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}
Jianwei Li, Samuel Robertshaw, Shouying Huang, Shelley Minteer, Xiaodong Wang
Nicotinamide adenine dinucleotide (NAD+) cofactor regeneration is essential for enabling dehydrogenase-promoted biosynthesis for value-added chemicals. Heterogeneous catalytic cofactor regeneration, using supported metal catalysts, is an emerging approach and has shown great promise. However, mechanistic insight remains largely unexplored. In this work, a series of silica-supported platinum (Pt) catalysts have been prepared for NAD+ cofactor regeneration, to understand the roles of Pt particle size and structure. A turnover frequency (TOF) ‘volcano plot’ was obtained over Pt clusters in the range of 2.2-7.1 nm, with the maximum TOF (136 h-1) observed at 5.6 nm. Selective Pt site blockage with polyvinyl pyrrolidone (PVP) revealed that the significant structure sensitivity originated from the synergistic effect of under- and well-coordinated sites over size-varied Pt clusters. In addition, a facet preference was also identified, where the cofactor regeneration favoured Pt(100) surface more than Pt(111). These findings provide the first insight into NAD+ regeneration on heterogeneous Pt catalysts, which will be particularly useful for the rational design of supported metal catalysts.
{"title":"Heterogeneous Catalysis of Large Biomolecules: Insights from Platinum Particle Size in NAD⁺ Regeneration","authors":"Jianwei Li, Samuel Robertshaw, Shouying Huang, Shelley Minteer, Xiaodong Wang","doi":"10.1039/d5cp03860j","DOIUrl":"https://doi.org/10.1039/d5cp03860j","url":null,"abstract":"Nicotinamide adenine dinucleotide (NAD+) cofactor regeneration is essential for enabling dehydrogenase-promoted biosynthesis for value-added chemicals. Heterogeneous catalytic cofactor regeneration, using supported metal catalysts, is an emerging approach and has shown great promise. However, mechanistic insight remains largely unexplored. In this work, a series of silica-supported platinum (Pt) catalysts have been prepared for NAD+ cofactor regeneration, to understand the roles of Pt particle size and structure. A turnover frequency (TOF) ‘volcano plot’ was obtained over Pt clusters in the range of 2.2-7.1 nm, with the maximum TOF (136 h-1) observed at 5.6 nm. Selective Pt site blockage with polyvinyl pyrrolidone (PVP) revealed that the significant structure sensitivity originated from the synergistic effect of under- and well-coordinated sites over size-varied Pt clusters. In addition, a facet preference was also identified, where the cofactor regeneration favoured Pt(100) surface more than Pt(111). These findings provide the first insight into NAD+ regeneration on heterogeneous Pt catalysts, which will be particularly useful for the rational design of supported metal catalysts.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"226 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728697","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}
Nguyen Thi Thao Le, Alireza Nazari, Yash Rele, Mighila Rixon, Ishudeep Narula, Matthew A. Addicoat
Reaction paths were calculated using Density Functional Theory for the reaction of carbon dioxide with a series of transition metal pentamers, M5 + CO2, (M = Nb, Mo, Ru, Rh, Pd, Ag, Pt). A stochastic search algorithm was used to identify geometries with intact CO2, as well as geometries where the CO2 molecule was partly (O + CO) and fully dissociated (O + C + O). Nb5 and Mo5 clusters were found to thermodynamically dissociate CO2. Pd5 and Ag5 were found to leave the CO2 molecule intact, Ru5 could partly dissociate CO2, while for Rh5 and Pt5, the fate of the adsorbed CO2 was dependent on the cluster geometry. The change in the CO2 πu orbital energy in the capture species on initial reaction with the M5 cluster was found to distinguish clusters where CO2 fully dissociated, but could not distinguish clusters where CO2 was found to partly dissociate.
利用密度泛函理论计算了二氧化碳与一系列过渡金属五聚体M5 + CO2 （M = Nb, Mo, Ru, Rh, Pd, Ag, Pt）的反应路径。使用随机搜索算法来识别具有完整CO2的几何形状，以及CO2分子部分（O + CO）和完全解离（O + C + O）的几何形状。发现Nb5和Mo5簇可以热力学解离CO2。发现Pd5和Ag5使CO2分子保持完整，Ru5可以部分解离CO2，而对于Rh5和Pt5，吸附CO2的命运取决于簇的几何形状。发现捕获物与M5簇初始反应时CO2 πu轨道能量的变化可以区分CO2完全解离的簇，但不能区分CO2部分解离的簇。
{"title":"Associative vs. dissociative binding of CO2 on M5 transition metal clusters","authors":"Nguyen Thi Thao Le, Alireza Nazari, Yash Rele, Mighila Rixon, Ishudeep Narula, Matthew A. Addicoat","doi":"10.1039/d5cp03418c","DOIUrl":"https://doi.org/10.1039/d5cp03418c","url":null,"abstract":"Reaction paths were calculated using Density Functional Theory for the reaction of carbon dioxide with a series of transition metal pentamers, M5 + CO2, (M = Nb, Mo, Ru, Rh, Pd, Ag, Pt). A stochastic search algorithm was used to identify geometries with intact CO2, as well as geometries where the CO2 molecule was partly (O + CO) and fully dissociated (O + C + O). Nb5 and Mo5 clusters were found to thermodynamically dissociate CO2. Pd5 and Ag5 were found to leave the CO2 molecule intact, Ru5 could partly dissociate CO2, while for Rh5 and Pt5, the fate of the adsorbed CO2 was dependent on the cluster geometry. The change in the CO2 πu orbital energy in the capture species on initial reaction with the M5 cluster was found to distinguish clusters where CO2 fully dissociated, but could not distinguish clusters where CO2 was found to partly dissociate.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704798","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}
We report the observation and assignment of the rotational spectra of the isotopically chiral molecule, trans-2,3-dideutero-oxirane (tc-CHDCHDO) measured with the Zurich gigahertz (GHz) spectrometer (64 to 500 GHz and Δν/ν = 10-11) and with our highest resolution Fourier transform infrared spectrometer at the Swiss synchrotron light source (SLS) (best instrumental resolution Δṽ = 0.00053 cm-1) in the terahertz range (far infrared from 25 to 80 cm-1). The combined GHz and THz spectra were analysed using an accurate effective Hamiltonian providing newly determined rotational parameters, which are crucial for the prediction of trans-2,3-dideutero-oxirane transitions to be observed by astrophysical spectroscopy. The recent detection of singly deuterated oxirane in the protostar IRAS 16 293-2422 B based on our previous predictions highlights the potential for the detection of doubly deuterated oxiranes including trans-2,3-dideutero-oxirane. These offer insights into deuterium fractionation in space and the formation mechanisms of complex and in particular chiral molecules. This study is also related to the new isotope effect in isotopically chiral molecules characterised by the parity violation energy differences of the ground states of the enantiomers and to biomolecular homochirality. In addition, we report the analysis of the pure rotational spectra of cis-2,3-dideutero-oxirane also present in our experimental spectra in the GHz range.
{"title":"Isotopic chirality and high-resolution gigahertz and terahertz spectroscopy of trans-2,3-dideutero-oxirane (tc-CHDCHDO).","authors":"Ziqiu Chen,Sieghard Albert,Karen Keppler,Gunther Wichmann,Martin Quack,Volker Schurig,Oliver Trapp","doi":"10.1039/d5cp03143e","DOIUrl":"https://doi.org/10.1039/d5cp03143e","url":null,"abstract":"We report the observation and assignment of the rotational spectra of the isotopically chiral molecule, trans-2,3-dideutero-oxirane (tc-CHDCHDO) measured with the Zurich gigahertz (GHz) spectrometer (64 to 500 GHz and Δν/ν = 10-11) and with our highest resolution Fourier transform infrared spectrometer at the Swiss synchrotron light source (SLS) (best instrumental resolution Δṽ = 0.00053 cm-1) in the terahertz range (far infrared from 25 to 80 cm-1). The combined GHz and THz spectra were analysed using an accurate effective Hamiltonian providing newly determined rotational parameters, which are crucial for the prediction of trans-2,3-dideutero-oxirane transitions to be observed by astrophysical spectroscopy. The recent detection of singly deuterated oxirane in the protostar IRAS 16 293-2422 B based on our previous predictions highlights the potential for the detection of doubly deuterated oxiranes including trans-2,3-dideutero-oxirane. These offer insights into deuterium fractionation in space and the formation mechanisms of complex and in particular chiral molecules. This study is also related to the new isotope effect in isotopically chiral molecules characterised by the parity violation energy differences of the ground states of the enantiomers and to biomolecular homochirality. In addition, we report the analysis of the pure rotational spectra of cis-2,3-dideutero-oxirane also present in our experimental spectra in the GHz range.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704442","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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