Chemical Physics最新文献

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Impact of terminal group on temperature-dependent excited state relaxation in cationic dyes

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-27 DOI: 10.1016/j.chemphys.2025.112620

Yuri Piryatinski , Anatoly Verbitsky , Markiian Malynovskyi , Aleksey Rozhin , Oleksiy Kachkovsky , Kateryna Maiko , Yuri Slominskii , Petro Lutsyk

Cationic organic dyes carry a positive charge distributed along the molecule, and the localization of this charge significantly affects their symmetry and optical properties. Depending on the different factors (topology of the terminal groups, the polarity of the solvent, and the temperature) the polyene, polymethine, or donor-acceptor structure form in such dyes, and excited state relaxation for such systems is not fully explored, particularly at low temperatures. At room temperature, the studied cationic dyes, regardless of symmetry in the ground state, are mostly symmetrical in the excited state. At low temperatures, charge localization effects become evident, leading to symmetry breaking in both ground and excited states. In this paper, we distinguish how terminal groups at the end of the cationic dyes impact the relaxation of excited states by analyzing experimental low-temperature time-resolved spectra combined with quantum-chemical calculations. Distinctive emission (690 nm) in the anti-Stokes range of polymethine band (700–730 nm) features polyene structures forming depending on the temperature, solvent polarity, and charge-donating properties of the dye's terminal groups. Furthermore, in low-temperature time-resolved photoluminescence, a 760 nm band is distinguished and associated with intramolecular charge transfer. Our calculations revealed unequal distribution of total positive charge in different molecular fragments (polymethine chain and terminal groups) and formation of negative charge on polymethine chain. We propose a model of excited state relaxation transitions for linear cationic molecular systems that enable donor-acceptor features. This model offers valuable insights for designing new functional materials with tunable properties or efficient energy transfer systems for artificial photosynthesis.

{"title":"Impact of terminal group on temperature-dependent excited state relaxation in cationic dyes","authors":"Yuri Piryatinski , Anatoly Verbitsky , Markiian Malynovskyi , Aleksey Rozhin , Oleksiy Kachkovsky , Kateryna Maiko , Yuri Slominskii , Petro Lutsyk","doi":"10.1016/j.chemphys.2025.112620","DOIUrl":"10.1016/j.chemphys.2025.112620","url":null,"abstract":"<div><div>Cationic organic dyes carry a positive charge distributed along the molecule, and the localization of this charge significantly affects their symmetry and optical properties. Depending on the different factors (topology of the terminal groups, the polarity of the solvent, and the temperature) the polyene, polymethine, or donor-acceptor structure form in such dyes, and excited state relaxation for such systems is not fully explored, particularly at low temperatures. At room temperature, the studied cationic dyes, regardless of symmetry in the ground state, are mostly symmetrical in the excited state. At low temperatures, charge localization effects become evident, leading to symmetry breaking in both ground and excited states. In this paper, we distinguish how terminal groups at the end of the cationic dyes impact the relaxation of excited states by analyzing experimental low-temperature time-resolved spectra combined with quantum-chemical calculations. Distinctive emission (690 nm) in the anti-Stokes range of polymethine band (700–730 nm) features polyene structures forming depending on the temperature, solvent polarity, and charge-donating properties of the dye's terminal groups. Furthermore, in low-temperature time-resolved photoluminescence, a 760 nm band is distinguished and associated with intramolecular charge transfer. Our calculations revealed unequal distribution of total positive charge in different molecular fragments (polymethine chain and terminal groups) and formation of negative charge on polymethine chain. We propose a model of excited state relaxation transitions for linear cationic molecular systems that enable donor-acceptor features. This model offers valuable insights for designing new functional materials with tunable properties or efficient energy transfer systems for artificial photosynthesis.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112620"},"PeriodicalIF":2.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Diffusion-thermo, Thermo-diffusion, Hall and ion slip effects on MHD flow through porous medium in a rotating channel

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-27 DOI: 10.1016/j.chemphys.2025.112623

M. Veera Krishna

The current study explored heat, mass, and electromagnetic forces interact in fluids, focusing on natural convective heat and mass transport in a three dimensional unsteady free convective boundary layer flow within a rotating vertical channel. It considers the effects of Soret and Dufour phenomena, viscous dissipation, suction, and Hall and ion slip effects. Using the Crank-Nicolson method, numerical results are found for velocity, temperature, and concentration are analyzed, with additional computations for skin friction, Nusselt, and Sherwood numbers. Key findings include increased velocity with Hall and ion slip effects, reduced thermal boundary layer thickness with higher Prandtl and suction parameters, and decreased concentration with higher Schmidt and suction parameters. Nusselt number and Sherwood number decrease with higher Soret parameter, but increase with stronger suction effects. Practical applications range from nuclear reactor cooling and thermoelectric power generation to groundwater pollutant modelling and geothermal energy enhancement, exploiting magnetic, thermal, and porous media effects. The most significant applications of the current study include cooling technologies and energy optimization in systems involving heat and mass transfer under magnetic and porous media effects. Also it is improving heat-to-electricity conversion efficiency by leveraging thermo-diffusion (Soret effect) and diffusion-thermo (Dufour effect).

{"title":"Diffusion-thermo, Thermo-diffusion, Hall and ion slip effects on MHD flow through porous medium in a rotating channel","authors":"M. Veera Krishna","doi":"10.1016/j.chemphys.2025.112623","DOIUrl":"10.1016/j.chemphys.2025.112623","url":null,"abstract":"<div><div>The current study explored heat, mass, and electromagnetic forces interact in fluids, focusing on natural convective heat and mass transport in a three dimensional unsteady free convective boundary layer flow within a rotating vertical channel. It considers the effects of Soret and Dufour phenomena, viscous dissipation, suction, and Hall and ion slip effects. Using the Crank-Nicolson method, numerical results are found for velocity, temperature, and concentration are analyzed, with additional computations for skin friction, Nusselt, and Sherwood numbers. Key findings include increased velocity with Hall and ion slip effects, reduced thermal boundary layer thickness with higher Prandtl and suction parameters, and decreased concentration with higher Schmidt and suction parameters. Nusselt number and Sherwood number decrease with higher Soret parameter, but increase with stronger suction effects. Practical applications range from nuclear reactor cooling and thermoelectric power generation to groundwater pollutant modelling and geothermal energy enhancement, exploiting magnetic, thermal, and porous media effects. The most significant applications of the current study include cooling technologies and energy optimization in systems involving heat and mass transfer under magnetic and porous media effects. Also it is improving heat-to-electricity conversion efficiency by leveraging thermo-diffusion (Soret effect) and diffusion-thermo (Dufour effect).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112623"},"PeriodicalIF":2.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143341637","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}

引用次数: 0

Near-IR range laser generation of refractive index gratings in O2 gas: Role of mono- and bimolecular absorption and collisional relaxation

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-27 DOI: 10.1016/j.chemphys.2025.112619

Dimitrii N. Kozlov

Laser-induced gratings (LIGs) were generated in neat O₂ at ambient temperature by photoexcitation of molecular species with nanosecond laser pulses at 1064 nm. LIGs were created at atmospheric pressure at different laser frequencies around that of the ^RR(11) transition of the O₂(a ¹Δ_g, υ = 1) ← O₂(X ³Σ_g⁻, υ = 0) absorption band of O₂ monomers, and over a wide pressure range (1–130 bar) at a fixed frequency. LIGs were probed by diffracting continuous wave laser radiation.

The proposed modeling indicates that at small delays (0–2 μs) LIGs are formed, in addition to electrostriction, by “instantaneous” collisional exchange of energy between the molecular species and the environment resulting from radiation absorption by O₂-O₂ dimols and the subsequent breakdown of the laser-excited species, with collisional emergence of electronically and vibrationally excited O₂ monomers. At large delays (20–1000 μs), LIGs are created by the “slow” collisional relaxation of the produced excited monomers.

{"title":"Near-IR range laser generation of refractive index gratings in O2 gas: Role of mono- and bimolecular absorption and collisional relaxation","authors":"Dimitrii N. Kozlov","doi":"10.1016/j.chemphys.2025.112619","DOIUrl":"10.1016/j.chemphys.2025.112619","url":null,"abstract":"<div><div>Laser-induced gratings (LIGs) were generated in neat O2 at ambient temperature by photoexcitation of molecular species with nanosecond laser pulses at 1064 nm. LIGs were created at atmospheric pressure at different laser frequencies around that of the RR(11) transition of the O2(a 1Δg, υ = 1) ← O2(X 3Σg−, υ = 0) absorption band of O2 monomers, and over a wide pressure range (1–130 bar) at a fixed frequency. LIGs were probed by diffracting continuous wave laser radiation.</div><div>The proposed modeling indicates that at small delays (0–2 μs) LIGs are formed, in addition to electrostriction, by “instantaneous” collisional exchange of energy between the molecular species and the environment resulting from radiation absorption by O2-O2 dimols and the subsequent breakdown of the laser-excited species, with collisional emergence of electronically and vibrationally excited O2 monomers. At large delays (20–1000 μs), LIGs are created by the “slow” collisional relaxation of the produced excited monomers.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112619"},"PeriodicalIF":2.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143341634","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}

引用次数: 0

Exploring superior photocatalytic behaviour of novel 2D/1D-NiFe2O4/Bi2O4 hybrid photocatalyst for efficacious degradation of methylene blue

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-23 DOI: 10.1016/j.chemphys.2025.112618

Parthasarathy Sasikala , Jagannathan Madhavan , Thirugnanam Bavani , Mani Preeyanghaa , Bernaurdshaw Neppolian

A promising visible-light driven photocatalyst Bi₂O₄ possess broadband spectral response range. Nevertheless, the speedy recombination of photogenerated e⁻/h⁺ pairs of bare Bi₂O₄ highly hampers its photocatalytic activities. An inverse spinel structure NiFe₂O4 has lesser photocatalytic activities but it owns ferromagnetic nature and virtuous chemical stability. These properties instigates to fabricate NiFe₂O₄/Bi₂O₄ composite. A series of NiFe₂O₄/Bi₂O₄ composites are obtained by distinct amount of NiFe₂O₄, via one-pot hydrothermal route. The optimized NiFe₂O₄/Bi₂O₄ nanocomposite contributed to an excellent photocatalytic degradation efficiency of 94 % for methylene blue (MB) under visible light irradiation after 60 min. The recycling experiment and radical trapping tests specified that the optimized NiFe₂O₄/Bi₂O₄ hybrid has highly stable and ensured the prominent capacity of the active species O₂^•− and ^•OH for photocatalytic degradation respectively. On the basis of above observations, a plausible mechanism of NiFe₂O₄/Bi₂O₄ composite towards the photocatalytic decomposition of MB under simulated VLI has been presented.

{"title":"Exploring superior photocatalytic behaviour of novel 2D/1D-NiFe2O4/Bi2O4 hybrid photocatalyst for efficacious degradation of methylene blue","authors":"Parthasarathy Sasikala , Jagannathan Madhavan , Thirugnanam Bavani , Mani Preeyanghaa , Bernaurdshaw Neppolian","doi":"10.1016/j.chemphys.2025.112618","DOIUrl":"10.1016/j.chemphys.2025.112618","url":null,"abstract":"<div><div>A promising visible-light driven photocatalyst Bi2O4 possess broadband spectral response range. Nevertheless, the speedy recombination of photogenerated e−/h+ pairs of bare Bi2O4 highly hampers its photocatalytic activities. An inverse spinel structure NiFe2O4 has lesser photocatalytic activities but it owns ferromagnetic nature and virtuous chemical stability. These properties instigates to fabricate NiFe2O4/Bi2O4 composite. A series of NiFe2O4/Bi2O4 composites are obtained by distinct amount of NiFe2O4, via one-pot hydrothermal route. The optimized NiFe2O4/Bi2O4 nanocomposite contributed to an excellent photocatalytic degradation efficiency of 94 % for methylene blue (MB) under visible light irradiation after 60 min. The recycling experiment and radical trapping tests specified that the optimized NiFe2O4/Bi2O4 hybrid has highly stable and ensured the prominent capacity of the active species O2•− and •OH for photocatalytic degradation respectively. On the basis of above observations, a plausible mechanism of NiFe2O4/Bi2O4 composite towards the photocatalytic decomposition of MB under simulated VLI has been presented.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112618"},"PeriodicalIF":2.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158559","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}

引用次数: 0

The potential application of zinc oxide nanotubes as sensors for NH3 detection: A DFT study

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-23 DOI: 10.1016/j.chemphys.2025.112614

Mohamed J. Saadh , Abdulrahman Qais Khaleel , Anjan Kumar , Pawan Sharma , Abhishek Kumar , Mohit Agarwal , Tatyana Orlova , Muna S. Merza , Mounir M. Bekhit , S. Islam

In recent years, nanostructured materials have played a key role in eliminating organic solvents from diverse mediums in various fields such as the fabrication of nano-adsorbents with high versatility. The dispersion corrected DFT approach was adopted within the current study to investigate the adhesion of NH₃ onto the pure ZnO nanotube (P-ZnONT) and Si-doped ZnONT (Si-ZnONT) since this approach is one of the powerful tools used to explore the nature of interactions and molecular systems at the atomic level. For this purpose, we investigated the interacting systems optimized geometric parameters as well as the active sites. By performing the ELF analysis and the calculation of charge transport, interaction energies and electronic attributes, the binding properties of interacting species are investigated to assess the capability of P-ZnONT and Si-ZnONT in adsorbing NH₃. Moreover, doping the Si atom enhanced the adhesion strength of the nanotubes dramatically. The results showed that SiZnONT was a suitable sensor to detect NH₃. The current findings can shed light into designing new nano-sensors as economical tolls for detecting pollutants in freshwater.

{"title":"The potential application of zinc oxide nanotubes as sensors for NH3 detection: A DFT study","authors":"Mohamed J. Saadh , Abdulrahman Qais Khaleel , Anjan Kumar , Pawan Sharma , Abhishek Kumar , Mohit Agarwal , Tatyana Orlova , Muna S. Merza , Mounir M. Bekhit , S. Islam","doi":"10.1016/j.chemphys.2025.112614","DOIUrl":"10.1016/j.chemphys.2025.112614","url":null,"abstract":"<div><div>In recent years, nanostructured materials have played a key role in eliminating organic solvents from diverse mediums in various fields such as the fabrication of nano-adsorbents with high versatility. The dispersion corrected DFT approach was adopted within the current study to investigate the adhesion of NH3 onto the pure ZnO nanotube (P-ZnONT) and Si-doped ZnONT (Si-ZnONT) since this approach is one of the powerful tools used to explore the nature of interactions and molecular systems at the atomic level. For this purpose, we investigated the interacting systems optimized geometric parameters as well as the active sites. By performing the ELF analysis and the calculation of charge transport, interaction energies and electronic attributes, the binding properties of interacting species are investigated to assess the capability of P-ZnONT and Si-ZnONT in adsorbing NH3. Moreover, doping the Si atom enhanced the adhesion strength of the nanotubes dramatically. The results showed that SiZnONT was a suitable sensor to detect NH3. The current findings can shed light into designing new nano-sensors as economical tolls for detecting pollutants in freshwater.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112614"},"PeriodicalIF":2.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158558","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}

引用次数: 0

3d transition metal anchored boron nitride edge for CO2 reduction reaction: A DFT study

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-22 DOI: 10.1016/j.chemphys.2025.112616

Wenlong Guo , Haiyue Liao , Wenhong Zeng , Xinlin Tang , Xin Lian , Peng Xiao , Guangyong Gao

The reduction mechanism of CO₂ on TM@BN (TM = Sc ∼ Zn) surface is investigated by density functional theory calculation. TM@BN (TM = Sc, V, Mn, Fe, Ni) are selected as potential catalysts by comparing the stability, CO₂ adsorption energy, selectivity and activity of CO₂RR. All potential reaction pathways and free energies of CO₂ conversion to C1 products are studied in detail. It is found that the protonation on C atom is more favorable than that on O atom. The results show that V@BN is a potential candidate catalyst for the production of CH₄, HCOOH and CH₃OH with limiting potentials of −0.82 V, −0.48 V and − 0.82 V, respectively.

引用次数: 0

First-principles calculation of electronic, vibrational, and thermodynamic properties of 5-amino-3-hydrazinyl-1H-1,2,4-triazole-based energetic materials

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-21 DOI: 10.1016/j.chemphys.2025.112605

Han-Ke Zhang , Qi-Jun Liu , Fu-Sheng Liu , Zheng-Tang Liu , Wen-Shuo Yuan

In recent years, nitrogen-rich energetic materials have attracted increasing attention due to their green and high-energy characteristics. It has been discovered that the overall properties of energetic ionic salts can be tuned by combining different cations and anions, as well as by introducing various functional groups. Therefore, research on nitrogen-rich energetic ionic materials is of great significance. In this study, the first-principles calculations were employed to investigate the newly constructed energetic ionic salt, 5-amino-3-hydrazinyl-1H-1,2,4-triazole. The electronic structure and vibrational properties of energetic salt 2 were calculated. The optimized lattice parameters obtained from our calculations are consistent with the literature data. The band structure and atomic projected density of states of energetic salt 2 were analyzed. Phonon dispersion curves and phonon density of states were plotted to analyze the phonon contributions. This study provides a reference for future research.

{"title":"First-principles calculation of electronic, vibrational, and thermodynamic properties of 5-amino-3-hydrazinyl-1H-1,2,4-triazole-based energetic materials","authors":"Han-Ke Zhang , Qi-Jun Liu , Fu-Sheng Liu , Zheng-Tang Liu , Wen-Shuo Yuan","doi":"10.1016/j.chemphys.2025.112605","DOIUrl":"10.1016/j.chemphys.2025.112605","url":null,"abstract":"<div><div>In recent years, nitrogen-rich energetic materials have attracted increasing attention due to their green and high-energy characteristics. It has been discovered that the overall properties of energetic ionic salts can be tuned by combining different cations and anions, as well as by introducing various functional groups. Therefore, research on nitrogen-rich energetic ionic materials is of great significance. In this study, the first-principles calculations were employed to investigate the newly constructed energetic ionic salt, 5-amino-3-hydrazinyl-1H-1,2,4-triazole. The electronic structure and vibrational properties of energetic salt 2 were calculated. The optimized lattice parameters obtained from our calculations are consistent with the literature data. The band structure and atomic projected density of states of energetic salt 2 were analyzed. Phonon dispersion curves and phonon density of states were plotted to analyze the phonon contributions. This study provides a reference for future research.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112605"},"PeriodicalIF":2.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158615","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}

引用次数: 0

Experimental and theoretical study of valence electron structure of cyclopentane: Electron momentum spectroscopy and molecular dynamics sampling

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-20 DOI: 10.1016/j.chemphys.2025.112613

Tuo Liu, Zhaohui Liu, Shanshan Niu, Enliang Wang, Yaguo Tang, Chunkai Xu, Xu Shan, Xiangjun Chen

We report a combined experimental and theoretical study on the valence electron structure of cyclopentane. The binding energy spectrum and electron momentum profiles were measured using a high-sensitivity (e, 2e) apparatus in symmetric non-coplanar kinematic arrangement at an incident energy of 1200 eV plus binding energy. To account for the vibrational effect, the experimental results were compared with the theoretical calculations based on the thermal sampling molecular dynamics (TSMD) method. The results show the significant influence of nuclear dynamics, including ring-puckering and pseudorotation, on the electron momentum profiles. The TSMD method, which incorporates all vibrational modes and full

Q

-space sampling, provides the best agreement with experiment, revealing the critical role of molecular vibrations in shaping the electronic structure of cyclopentane.

引用次数: 0

Selective adsorption of uranium(VI) by clay minerals from saline conditions: Molecular dynamics simulations

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-17 DOI: 10.1016/j.chemphys.2025.112610

Sen Yang, Gang Yang

Uranium represents one of the most radioactive and toxic metals. A systematic study of UO₂²⁺ adsorption by clay minerals is conducted using molecular dynamics, especially from highly saline conditions where a majority of uranium is detected. UO₂²⁺ adsorption and exchange occur favorably at basal rather than other surfaces. Clay minerals, especially beidellite, are UO₂²⁺-selective, and adsorption selectivity increases at higher salinity. Adsorption and selectivity are regulated by charge location and surface structure, and enhanced by temperature elevation, showing stronger coupling at higher UO₂²⁺ concentrations. Co-existing metal ions affect UO₂²⁺ adsorption more than anions, and thermodynamic preference of cation exchange follows as Ca²⁺ > K⁺ > Na⁺ and CO₃²⁻ > Cl⁻ while kinetic preference has reversed trends. Higher CO₃²⁻ concentrations are necessary for coupling with Na⁺ vs. Ca²⁺. Results promote the understanding of UO₂²⁺ adsorption by clay materials, and are beneficial to uranium contamination management and nuclear fuels utilization.

{"title":"Selective adsorption of uranium(VI) by clay minerals from saline conditions: Molecular dynamics simulations","authors":"Sen Yang, Gang Yang","doi":"10.1016/j.chemphys.2025.112610","DOIUrl":"10.1016/j.chemphys.2025.112610","url":null,"abstract":"<div><div>Uranium represents one of the most radioactive and toxic metals. A systematic study of UO22+ adsorption by clay minerals is conducted using molecular dynamics, especially from highly saline conditions where a majority of uranium is detected. UO22+ adsorption and exchange occur favorably at basal rather than other surfaces. Clay minerals, especially beidellite, are UO22+-selective, and adsorption selectivity increases at higher salinity. Adsorption and selectivity are regulated by charge location and surface structure, and enhanced by temperature elevation, showing stronger coupling at higher UO22+ concentrations. Co-existing metal ions affect UO22+ adsorption more than anions, and thermodynamic preference of cation exchange follows as Ca2+ > K+ > Na+ and CO32− > Cl− while kinetic preference has reversed trends. Higher CO32− concentrations are necessary for coupling with Na+ vs. Ca2+. Results promote the understanding of UO22+ adsorption by clay materials, and are beneficial to uranium contamination management and nuclear fuels utilization.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112610"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158612","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}

引用次数: 0

Study of the difference in floatability between quartz and feldspar based on first principles

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-01-17 DOI: 10.1016/j.chemphys.2025.112612

Caixia Li , Yi Xu , Ruize Liu , Mingxuan Dou , Yang Bai , Zengchuan Yue , Qianyu Sun , Wanzhong Yin

For the initial time, this research juxtaposes the surface atomic activities of quartz and potassium feldspar, centering on their respective surface atomic relaxation distances. Findings indicate that on quartz surfaces, the primary adsorption locales are unsaturated Si atoms paired with dangling O atoms. Conversely, the feldspar surface’s key adsorption points involve tri-coordinated Al atoms alongside hanging O atoms. Water molecules on feldspar’s Al, K, and O sites form various bonds—covalent, ionic, and hydrogen. On the quartz counterpart, water molecules exclusively interact with Si and O atoms, with each Si atom accommodating a single water molecule, thus rendering the potassium feldspar’s surface more conducive to wetting—a finding corroborated by the contact angle experiments. Within a sodium oleate matrix, oleate anions link to quartz via hydrogen bonds, whereas they attach to feldspar surfaces forming mono-component rings through both covalent and ionic bonding.

引用次数: 0

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