Ronghui Sun,Zhen Fan,Xin Zheng,Changyu Sun,Shouwei Zhou,Qingping Li
The influences of NaCl concentrations from 1-5 mol% on the growth kinetics of CO2 hydrates and the structural characteristics of the formed solid products were investigated through molecular dynamics simulations. Lower temperatures and higher NaCl concentrations exhibited increasing inhibition effects on hydrate growth. Small numbers of Cl- anions constituted distorted edge-sharing host cages while minority Na+ cations tended to behave as hopping guests shuttling among host cages. NaCl crystallites were observed, suggesting both the carbon storage capability in the hydrate even from highly salty solutions and the presence of solid NaCl inclusions within polycrystalline hydrate entities, necessitating practical considerations in potential industrial processes such as oceanic carbon storage and desalination.
{"title":"Molecular dynamics simulation study on the growth of CO2 hydrate from high-concentration NaCl solutions.","authors":"Ronghui Sun,Zhen Fan,Xin Zheng,Changyu Sun,Shouwei Zhou,Qingping Li","doi":"10.1039/d5cp03116h","DOIUrl":"https://doi.org/10.1039/d5cp03116h","url":null,"abstract":"The influences of NaCl concentrations from 1-5 mol% on the growth kinetics of CO2 hydrates and the structural characteristics of the formed solid products were investigated through molecular dynamics simulations. Lower temperatures and higher NaCl concentrations exhibited increasing inhibition effects on hydrate growth. Small numbers of Cl- anions constituted distorted edge-sharing host cages while minority Na+ cations tended to behave as hopping guests shuttling among host cages. NaCl crystallites were observed, suggesting both the carbon storage capability in the hydrate even from highly salty solutions and the presence of solid NaCl inclusions within polycrystalline hydrate entities, necessitating practical considerations in potential industrial processes such as oceanic carbon storage and desalination.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759917","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}
Abid Ali,Anastasiia S Kozlenko,Ilya V Ozhogin,Tomas Vincze,Martin Weis,Farman Ali
We report a comprehensive investigation of the anti-Kasha phenomenon in 2-(2,6-bis((E)-2-(pyren-1-yl)vinyl)-4H-pyran-4-ylidene)malononitrile (DCM-Py). This was a promising dual-emissive fluorophore exhibiting simultaneous blue and orange emission in solution with quantum yield up to 30%. Through state-of-the-art experimental characterization and quantum chemical modeling, we revealed genuine anti-Kasha behavior by systematically excluding potential artifacts. The unique photophysical properties of DCM-Py were harnessed in functional organic light-emitting diode (OLED) prototypes, demonstrating dual bands in the electroluminescence spectrum and yellow emission in a device. The electrically generated exciton in the device had a similar channel to relax to ground state as in solution, indicative of a multi-state exciton relaxation pathway in the emissive layer (DCM-Py), further showcasing an anti-Kasha property.
{"title":"Investigating unusual photoluminescence from the excited state in a DCM derivative and its application in lighting devices.","authors":"Abid Ali,Anastasiia S Kozlenko,Ilya V Ozhogin,Tomas Vincze,Martin Weis,Farman Ali","doi":"10.1039/d5cp03290c","DOIUrl":"https://doi.org/10.1039/d5cp03290c","url":null,"abstract":"We report a comprehensive investigation of the anti-Kasha phenomenon in 2-(2,6-bis((E)-2-(pyren-1-yl)vinyl)-4H-pyran-4-ylidene)malononitrile (DCM-Py). This was a promising dual-emissive fluorophore exhibiting simultaneous blue and orange emission in solution with quantum yield up to 30%. Through state-of-the-art experimental characterization and quantum chemical modeling, we revealed genuine anti-Kasha behavior by systematically excluding potential artifacts. The unique photophysical properties of DCM-Py were harnessed in functional organic light-emitting diode (OLED) prototypes, demonstrating dual bands in the electroluminescence spectrum and yellow emission in a device. The electrically generated exciton in the device had a similar channel to relax to ground state as in solution, indicative of a multi-state exciton relaxation pathway in the emissive layer (DCM-Py), further showcasing an anti-Kasha property.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"156 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759918","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}
Ru(II) complexes have been explored as promising candidates for novel anticancer agents, due to their significant bioactivity, selective cytotoxicity, and ability to induce apoptosis via multiple signalling pathways, with coumarin derivatives serving as effective ligands to enhance their therapeutic efficacy. DFT calculations are highly useful in comprehensively analyzing the electronic structures, and physicochemical and thermodynamic properties of these metal complexes. For example, MEP maps are used to visualize the molecular charge distribution, while NBO analysis is employed to investigate the charge transfer interactions. The donor-acceptor behaviour of the metal-ligand complexes is also examined to gain deeper insights into their electronic properties and potential reactivity. QTAIM analysis confirms that weak H-bonding and vdW interactions significantly stabilize the studied adducts, particularly [RuCl2(yc4)2(DMSO)2]·2H2O and AT/GC base pair complexes. Molecular docking is further employed to investigate the DNA-binding affinity and interaction mechanisms of these complexes, with a specific focus on AT/GC nucleobases. The molecular docking results provide insights into the stability of the adducts and reveal their preferred binding sites within DNA nucleobases. Finally, molecular dynamics simulation calculations were employed to complement DFT and docking analyses. Again, MM/PBSA free energy and H-bond analyses indicate stronger thermodynamic interactions of the [RuCl2(yc4)2(DMSO)2]·2H2O complex with AT-rich regions. Hence, this in silico study on Ru(II)-coumarin complexes offers valuable insights for the rational design of metal-based anticancer therapeutics.
{"title":"Computational insights into Ru(II)-coumarin complexes as potential anticancer agents: a DFT, QTAIM, NCI-RDG, molecular docking and molecular dynamics approach.","authors":"Pratyashee Barukial,Rajib Nandi,Manazira Ahmed,Rituraj Barman,Tamal Banerjee,Bipul Bezbaruah","doi":"10.1039/d5cp03171k","DOIUrl":"https://doi.org/10.1039/d5cp03171k","url":null,"abstract":"Ru(II) complexes have been explored as promising candidates for novel anticancer agents, due to their significant bioactivity, selective cytotoxicity, and ability to induce apoptosis via multiple signalling pathways, with coumarin derivatives serving as effective ligands to enhance their therapeutic efficacy. DFT calculations are highly useful in comprehensively analyzing the electronic structures, and physicochemical and thermodynamic properties of these metal complexes. For example, MEP maps are used to visualize the molecular charge distribution, while NBO analysis is employed to investigate the charge transfer interactions. The donor-acceptor behaviour of the metal-ligand complexes is also examined to gain deeper insights into their electronic properties and potential reactivity. QTAIM analysis confirms that weak H-bonding and vdW interactions significantly stabilize the studied adducts, particularly [RuCl2(yc4)2(DMSO)2]·2H2O and AT/GC base pair complexes. Molecular docking is further employed to investigate the DNA-binding affinity and interaction mechanisms of these complexes, with a specific focus on AT/GC nucleobases. The molecular docking results provide insights into the stability of the adducts and reveal their preferred binding sites within DNA nucleobases. Finally, molecular dynamics simulation calculations were employed to complement DFT and docking analyses. Again, MM/PBSA free energy and H-bond analyses indicate stronger thermodynamic interactions of the [RuCl2(yc4)2(DMSO)2]·2H2O complex with AT-rich regions. Hence, this in silico study on Ru(II)-coumarin complexes offers valuable insights for the rational design of metal-based anticancer therapeutics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"21 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759919","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}
Boron-based nanomaterials have been considered as potential candidates for hydrogen storage due to their unique electronic properties. In this work, we constructed a two-dimensional superatomic B12N2 monolayer for hydrogen storage by substituting all atoms in T-MoS2 monolayers with icosahedral B12 units and N atoms. Chemical bonding analysis confirms that the B12 unit follows Wade's rule (2n + 2), exhibiting a 1S21P61D101F8 superatomic configuration with 13 highly delocalized twelve-centre two-electron (12c-2e) orbitals. Further studies reveal that the adsorption energy of one H2 molecule is markedly improved from -0.08 eV (pristine) to -0.33 eV upon Li decoration, driven by polarization via Li-to-monolayer charge transfer. The 2 × 2 × 1 B48N8 supercell can hold 8 Li atoms and 32 H2 molecules, achieving a maximum hydrogen storage capacity of 8.60 wt% over the DOE target (6.5 wt%) in 2025. The calculated desorption temperature and molecular dynamics simulations further demonstrate that the Li-decorated B12N2 monolayer can be regarded as a reversible hydrogen storage material at elevated pressure and/or reduced temperature. Moreover, the importance of zero-point energy effects for hydrogen storage calculation is discussed by comparing the changes in H2 adsorption ability.
{"title":"A first-principles study of hydrogen storage on pristine and Li-decorated superatomic B12N2 monolayers.","authors":"Qinqin Yuan,Zicheng Ling,Zaijun Gui,Lili Shi,Dan Li,Longjiu Cheng","doi":"10.1039/d5cp03844h","DOIUrl":"https://doi.org/10.1039/d5cp03844h","url":null,"abstract":"Boron-based nanomaterials have been considered as potential candidates for hydrogen storage due to their unique electronic properties. In this work, we constructed a two-dimensional superatomic B12N2 monolayer for hydrogen storage by substituting all atoms in T-MoS2 monolayers with icosahedral B12 units and N atoms. Chemical bonding analysis confirms that the B12 unit follows Wade's rule (2n + 2), exhibiting a 1S21P61D101F8 superatomic configuration with 13 highly delocalized twelve-centre two-electron (12c-2e) orbitals. Further studies reveal that the adsorption energy of one H2 molecule is markedly improved from -0.08 eV (pristine) to -0.33 eV upon Li decoration, driven by polarization via Li-to-monolayer charge transfer. The 2 × 2 × 1 B48N8 supercell can hold 8 Li atoms and 32 H2 molecules, achieving a maximum hydrogen storage capacity of 8.60 wt% over the DOE target (6.5 wt%) in 2025. The calculated desorption temperature and molecular dynamics simulations further demonstrate that the Li-decorated B12N2 monolayer can be regarded as a reversible hydrogen storage material at elevated pressure and/or reduced temperature. Moreover, the importance of zero-point energy effects for hydrogen storage calculation is discussed by comparing the changes in H2 adsorption ability.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752780","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}
7,12-Dimethylbenz[a]anthracene (DMBA) is a significant environmental pollutant belonging to the class of methylated polycyclic aromatic hydrocarbons (MPAHs). It is generated via the incomplete combustion of organic compounds and can induce cancer in a variety of organisms. Therefore, strengthening the study of DMBA metabolism and understanding its potential hazards to human health are of great significance. In this study, human CYP1B1 was employed as the metabolic enzyme to investigate the binding modes, reaction sites and metabolic mechanisms of DMBA by molecular docking, molecular dynamics (MD) simulations and quantum mechanical (QM) calculations. Results indicated that DMBA binds to the active site of CYP1B1 primarily through nonpolar solvation energies (ΔGnonpolar) in two modes. The π-π interactions formed by Phe231 and Phe268 with DMBA constituted a "sandwich" structure, which acted as a critical stabilizing element in both modes. In both modes, DMBA was metabolized by an electrophilic addition-rearrangement mechanism. Notably, C3 was the electrophilic addition site in mode I, while in mode II, the extra amide-π interaction between Gly329 and DMBA made C4 the preferred metabolic site. Consequently, in path II, the electrophilic addition-rearrangement metabolic process at the C4 site in mode II became the relatively favored metabolic pathway. These results provide theoretical insights into the biological metabolic processes of DMBA and contribute to the comprehension of its toxification potential and cancer risks.
{"title":"Origin of the metabolic site selectivity of 7,12-dimethylbenz[a]anthracene catalysed by the P450 1B1 cytochrome: an in silico protocol.","authors":"Chong Liu,Yan Zhao,Shi Feng,Qingchuan Zheng","doi":"10.1039/d5cp04154f","DOIUrl":"https://doi.org/10.1039/d5cp04154f","url":null,"abstract":"7,12-Dimethylbenz[a]anthracene (DMBA) is a significant environmental pollutant belonging to the class of methylated polycyclic aromatic hydrocarbons (MPAHs). It is generated via the incomplete combustion of organic compounds and can induce cancer in a variety of organisms. Therefore, strengthening the study of DMBA metabolism and understanding its potential hazards to human health are of great significance. In this study, human CYP1B1 was employed as the metabolic enzyme to investigate the binding modes, reaction sites and metabolic mechanisms of DMBA by molecular docking, molecular dynamics (MD) simulations and quantum mechanical (QM) calculations. Results indicated that DMBA binds to the active site of CYP1B1 primarily through nonpolar solvation energies (ΔGnonpolar) in two modes. The π-π interactions formed by Phe231 and Phe268 with DMBA constituted a \"sandwich\" structure, which acted as a critical stabilizing element in both modes. In both modes, DMBA was metabolized by an electrophilic addition-rearrangement mechanism. Notably, C3 was the electrophilic addition site in mode I, while in mode II, the extra amide-π interaction between Gly329 and DMBA made C4 the preferred metabolic site. Consequently, in path II, the electrophilic addition-rearrangement metabolic process at the C4 site in mode II became the relatively favored metabolic pathway. These results provide theoretical insights into the biological metabolic processes of DMBA and contribute to the comprehension of its toxification potential and cancer risks.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752800","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}
Arnab Choudhury, Felix Graber, Stefan Feusi, Jan Krohn, Jai Khatri, Fernando Torres-Hernandez, Chenxi Li, Ruth Signorell
Carbon dioxide (CO2) gas is known to strongly accelerate nucleation of other gas phase components, such as water and toluene. The acceleration was attributed to the formation of transient heteromolecular dimers and referred to as the chaperon mechanism. In this work, we investigate this phenomenon for butane-CO2 gas mixtures with mass spectrometry in the post-nozzle flow of a Laval expansion at a temperature of 51 K and a pressure of 40 Pa. At moderate CO2 and butane concentrations, we observed an acceleration of butane nucleation by the chaperon mechanism, albeit only by a factor of about two compared to unary butane nucleation. The fact that the chaperon mechanism is less important for butane than for water and toluene can be rationalized by the weaker intermolecular interactions between butane and CO2. At higher CO2 and butane concentrations, nucleation and cluster growth overlap in time, which leads to saturation of the measured total butane concentration. Using a kinetic model, we show that saturation is caused by the formation of heteromolecular butane-CO2 clusters of different sizes and compositions. Studies on nucleation at low temperatures in such systems are relevant for flue or natural gas separation.
{"title":"Acceleration of Butane Vapor Nucleation by Carbon Dioxide Gas","authors":"Arnab Choudhury, Felix Graber, Stefan Feusi, Jan Krohn, Jai Khatri, Fernando Torres-Hernandez, Chenxi Li, Ruth Signorell","doi":"10.1039/d5cp03900b","DOIUrl":"https://doi.org/10.1039/d5cp03900b","url":null,"abstract":"Carbon dioxide (CO2) gas is known to strongly accelerate nucleation of other gas phase components, such as water and toluene. The acceleration was attributed to the formation of transient heteromolecular dimers and referred to as the chaperon mechanism. In this work, we investigate this phenomenon for butane-CO2 gas mixtures with mass spectrometry in the post-nozzle flow of a Laval expansion at a temperature of 51 K and a pressure of 40 Pa. At moderate CO2 and butane concentrations, we observed an acceleration of butane nucleation by the chaperon mechanism, albeit only by a factor of about two compared to unary butane nucleation. The fact that the chaperon mechanism is less important for butane than for water and toluene can be rationalized by the weaker intermolecular interactions between butane and CO2. At higher CO2 and butane concentrations, nucleation and cluster growth overlap in time, which leads to saturation of the measured total butane concentration. Using a kinetic model, we show that saturation is caused by the formation of heteromolecular butane-CO2 clusters of different sizes and compositions. Studies on nucleation at low temperatures in such systems are relevant for flue or natural gas separation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"151 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753268","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}
Abdul Zeeshan Khan,Muhammad Shafi,Tarek A Kandiel,Abdulaziz A Al-Saadi
Hybrid organic-inorganic perovskites (HOIPs) have emerged as a transformative photovoltaic technology, achieving remarkable efficiency improvement in solar cell applications. However, the stability of perovskite-based materials remains a key issue and thus requires advanced non-destructive characterization methods. Raman spectroscopy, owing to its sensitivity to molecular and structural changes, is a promising tool for probing the surface characteristics of perovskite materials and for providing valuable insights into their vibrational properties and phase transition behavior. In this study, both in situ and ex situ Raman spectroscopy were employed to investigate the transition of solvated methylammonium iodide (MAI) and PbI2 to MAPbI3 perovskite crystals. The crystalline MAPbI3 phase formed at 60 °C exhibited no distinct first-order Raman modes under 532 and 633 nm excitations, depicting its Raman inactivity under these conditions. Weak scattering features observed using a 785 nm laser can be attributed to the dynamic reorientation of methylammonium cations. These conclusions were supported by spectral measurements conducted under inert and atmospheric conditions at various power levels.
{"title":"Spectroscopic investigation of the solvated MAPbI3 transition to perovskite crystals: a temperature-dependent Raman study.","authors":"Abdul Zeeshan Khan,Muhammad Shafi,Tarek A Kandiel,Abdulaziz A Al-Saadi","doi":"10.1039/d5cp04336k","DOIUrl":"https://doi.org/10.1039/d5cp04336k","url":null,"abstract":"Hybrid organic-inorganic perovskites (HOIPs) have emerged as a transformative photovoltaic technology, achieving remarkable efficiency improvement in solar cell applications. However, the stability of perovskite-based materials remains a key issue and thus requires advanced non-destructive characterization methods. Raman spectroscopy, owing to its sensitivity to molecular and structural changes, is a promising tool for probing the surface characteristics of perovskite materials and for providing valuable insights into their vibrational properties and phase transition behavior. In this study, both in situ and ex situ Raman spectroscopy were employed to investigate the transition of solvated methylammonium iodide (MAI) and PbI2 to MAPbI3 perovskite crystals. The crystalline MAPbI3 phase formed at 60 °C exhibited no distinct first-order Raman modes under 532 and 633 nm excitations, depicting its Raman inactivity under these conditions. Weak scattering features observed using a 785 nm laser can be attributed to the dynamic reorientation of methylammonium cations. These conclusions were supported by spectral measurements conducted under inert and atmospheric conditions at various power levels.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"169 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752778","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 research explores the capability of lithium-modified pristine and defect-engineered B3C2N3 monolayers (VB, VC, and VN) for hydrogen storage, employing periodic DFT calculations. Several key metrics were evaluated, including the adsorption and binding energies of lithium atoms and H2 molecules on these substrates, storage capacity, desorption temperatures, electronic characteristics, and the molecular stability of the structures. The findings reveal that the most thermodynamically favorable configuration comprises eight lithium atoms, yielding an optimal adsorption energy of -0.199 eV per H2 molecule in the final state, designated as 20H2@8Li-VC. This configuration further exhibits a gravimetric hydrogen storage capacity of 8.4 wt% and enables hydrogen desorption at approximately 256 K. The investigation of the dynamic and thermal characteristics of the 8Li-VC system, conducted through ab initio molecular dynamics simulations, provides valuable insights and guidance for future efforts aimed at utilizing this monolayer in hydrogen storage applications with the 8Li-VC arrangement.
{"title":"B3C2N3 monolayer with vacancy defects decorated with lithium as a potential hydrogen storage system: a DFT study.","authors":"Rezvan Rahimi,Mohammad Solimannejad,Yafei Zhang","doi":"10.1039/d5cp03468j","DOIUrl":"https://doi.org/10.1039/d5cp03468j","url":null,"abstract":"This research explores the capability of lithium-modified pristine and defect-engineered B3C2N3 monolayers (VB, VC, and VN) for hydrogen storage, employing periodic DFT calculations. Several key metrics were evaluated, including the adsorption and binding energies of lithium atoms and H2 molecules on these substrates, storage capacity, desorption temperatures, electronic characteristics, and the molecular stability of the structures. The findings reveal that the most thermodynamically favorable configuration comprises eight lithium atoms, yielding an optimal adsorption energy of -0.199 eV per H2 molecule in the final state, designated as 20H2@8Li-VC. This configuration further exhibits a gravimetric hydrogen storage capacity of 8.4 wt% and enables hydrogen desorption at approximately 256 K. The investigation of the dynamic and thermal characteristics of the 8Li-VC system, conducted through ab initio molecular dynamics simulations, provides valuable insights and guidance for future efforts aimed at utilizing this monolayer in hydrogen storage applications with the 8Li-VC arrangement.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145759988","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}
Water interfaces play critical roles in numerous physicochemical processes, with significant implications for green energy, atmospheric science, materials research, biological systems, and chemical reactions. Sum-frequency vibrational spectroscopy (SFVS) is a sensitive and selective nonlinear technique for probing interfacial molecular orientations, structures, and dynamics in situ. By combining ab initio molecular dynamics simulations and quantum chemistry calculations—which explicitly account for electronic quantum effects—we compute the imaginary part of the SSP SFVS for interfacial water. Our results demonstrate that the shoulder peak of the free OH group stems from both the electric quadrupole and magnetic dipole contributions, with the former being dominant. This approach balances simplicity with physical rigor, potentially offering a new theoretical framework for interpreting complex SFVS.
{"title":"Origin of the shoulder peak in sum-frequency vibrational spectroscopy of interfacial water","authors":"Ren-Hui Zheng, Wen-Mei Wei, Chao-Long Liang","doi":"10.1039/d5cp03920g","DOIUrl":"https://doi.org/10.1039/d5cp03920g","url":null,"abstract":"Water interfaces play critical roles in numerous physicochemical processes, with significant implications for green energy, atmospheric science, materials research, biological systems, and chemical reactions. Sum-frequency vibrational spectroscopy (SFVS) is a sensitive and selective nonlinear technique for probing interfacial molecular orientations, structures, and dynamics in situ. By combining ab initio molecular dynamics simulations and quantum chemistry calculations—which explicitly account for electronic quantum effects—we compute the imaginary part of the SSP SFVS for interfacial water. Our results demonstrate that the shoulder peak of the free OH group stems from both the electric quadrupole and magnetic dipole contributions, with the former being dominant. This approach balances simplicity with physical rigor, potentially offering a new theoretical framework for interpreting complex SFVS.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753267","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}
A L Danilyuk,D A Podryabinkin,A B Filonov,G A Ovsyannikov,G D Ulev,K Y Constantinian,D B Migas
The magnetoresistance and Hall resistance of thin epitaxial SrIrO3 films were measured at 2 K and 10 K in magnetic fields of up to 10 T, and negative magnetoresistances of 2-4% were obtained. In order to reproduce and correctly describe the experimental data, the quantum contributions to the magnetoconductivity due to spin splitting, Coulomb interaction, and weak localization/antilocalization for 3D disordered metal systems were estimated for the first time. It was shown that the increase in the magnetoconductivity was mainly caused by weak localization, which was suppressed by the magnetic field, leading to weak anti-localization, and by the phonon-induced electron attraction.
{"title":"Role of quantum contributions in the magnetoconductance behavior of iridate films at low temperatures.","authors":"A L Danilyuk,D A Podryabinkin,A B Filonov,G A Ovsyannikov,G D Ulev,K Y Constantinian,D B Migas","doi":"10.1039/d5cp03094c","DOIUrl":"https://doi.org/10.1039/d5cp03094c","url":null,"abstract":"The magnetoresistance and Hall resistance of thin epitaxial SrIrO3 films were measured at 2 K and 10 K in magnetic fields of up to 10 T, and negative magnetoresistances of 2-4% were obtained. In order to reproduce and correctly describe the experimental data, the quantum contributions to the magnetoconductivity due to spin splitting, Coulomb interaction, and weak localization/antilocalization for 3D disordered metal systems were estimated for the first time. It was shown that the increase in the magnetoconductivity was mainly caused by weak localization, which was suppressed by the magnetic field, leading to weak anti-localization, and by the phonon-induced electron attraction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752802","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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