Chemical Physics最新文献

{"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 ^<em>R</em><em>R</em>(11) transition of the O₂(<em>a</em> ¹Δ_<em>g</em>, <em>υ</em> = 1) ← O₂(<em>X</em> ³Σ_<em>g</em>⁻, <em>υ</em> = 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}

{"title":"Exploring superior photocatalytic behaviour of novel 2D/1D-NiFe2O4/Bi2O4 hybrid photocatalyst for efficacious degradation of methylene blue","authors":"Parthasarathy Sasikala ,&nbsp;Jagannathan Madhavan ,&nbsp;Thirugnanam Bavani ,&nbsp;Mani Preeyanghaa ,&nbsp;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}

{"title":"The potential application of zinc oxide nanotubes as sensors for NH3 detection: A DFT study","authors":"Mohamed J. Saadh ,&nbsp;Abdulrahman Qais Khaleel ,&nbsp;Anjan Kumar ,&nbsp;Pawan Sharma ,&nbsp;Abhishek Kumar ,&nbsp;Mohit Agarwal ,&nbsp;Tatyana Orlova ,&nbsp;Muna S. Merza ,&nbsp;Mounir M. Bekhit ,&nbsp;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}

{"title":"3d transition metal anchored boron nitride edge for CO2 reduction reaction: A DFT study","authors":"Wenlong Guo ,&nbsp;Haiyue Liao ,&nbsp;Wenhong Zeng ,&nbsp;Xinlin Tang ,&nbsp;Xin Lian ,&nbsp;Peng Xiao ,&nbsp;Guangyong Gao","doi":"10.1016/j.chemphys.2025.112616","DOIUrl":"10.1016/j.chemphys.2025.112616","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112616"},"PeriodicalIF":2.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158617","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}

{"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 ,&nbsp;Qi-Jun Liu ,&nbsp;Fu-Sheng Liu ,&nbsp;Zheng-Tang Liu ,&nbsp;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}

{"title":"Experimental and theoretical study of valence electron structure of cyclopentane: Electron momentum spectroscopy and molecular dynamics sampling","authors":"Tuo Liu,&nbsp;Zhaohui Liu,&nbsp;Shanshan Niu,&nbsp;Enliang Wang,&nbsp;Yaguo Tang,&nbsp;Chunkai Xu,&nbsp;Xu Shan,&nbsp;Xiangjun Chen","doi":"10.1016/j.chemphys.2025.112613","DOIUrl":"10.1016/j.chemphys.2025.112613","url":null,"abstract":"<div><div>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 <span><math><mi>Q</mi></math></span>-space sampling, provides the best agreement with experiment, revealing the critical role of molecular vibrations in shaping the electronic structure of cyclopentane.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112613"},"PeriodicalIF":2.0,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158557","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}

{"title":"Selective adsorption of uranium(VI) by clay minerals from saline conditions: Molecular dynamics simulations","authors":"Sen Yang,&nbsp;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⁺ &gt; K⁺ &gt; Na⁺ and CO₃²⁻ &gt; 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}

{"title":"Study of the difference in floatability between quartz and feldspar based on first principles","authors":"Caixia Li ,&nbsp;Yi Xu ,&nbsp;Ruize Liu ,&nbsp;Mingxuan Dou ,&nbsp;Yang Bai ,&nbsp;Zengchuan Yue ,&nbsp;Qianyu Sun ,&nbsp;Wanzhong Yin","doi":"10.1016/j.chemphys.2025.112612","DOIUrl":"10.1016/j.chemphys.2025.112612","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112612"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158614","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}

{"title":"The role of heavy atom effect in regulating multiple-resonance and thermally activated delayed fluorescence features: A theoretical perspective","authors":"Xuelu Yang ,&nbsp;Songsong Liu ,&nbsp;Yang Gao ,&nbsp;Lili Lin ,&nbsp;Chuan-Kui Wang ,&nbsp;Jianzhong Fan ,&nbsp;Yuzhi Song","doi":"10.1016/j.chemphys.2025.112611","DOIUrl":"10.1016/j.chemphys.2025.112611","url":null,"abstract":"<div><div>Multiple-resonance thermally activated delayed fluorescence (MR-TADF) emitters with high efficiency and narrowband emission characteristics have shown wide applications in organic light-emitting diodes. However, MR-TADF emitters usually exhibit slow reverse intersystem crossing (RISC) rates, the amount and species of efficient MR-TADF emitters are limited, corresponding structure–property relationship needs to be clarified. Herein, based on density functional theory, time-dependent density functional theory and SCS-ADC(2) method, five reported MR-TADF molecules (CzBO, CzBS, CzBSe, Cz-PTZ-BN and BN-Se) are adopted and their photophysical properties are studied by thermal vibration correlation function (TVCF) method, the heavy atom effect on increasing spin–orbit coupling (SOC) and thus accelerating RISC process is elucidated. Based on this strategy with π-conjugated extension of MR unit, four new molecules (wBN-O, wCz-PTZ-BN, wBN-Se and BN-O) are theoretically proposed and their full-width at half-maximum (FWHM) values and excited decay rates are calculated. Results indicate that all studied molecules possess small energy gaps (ΔE_ST) between <em>S₁</em> and <em>T₁</em>, and they are corresponding well with experimental values. In addition, large SOC constants are determined for designed molecules, remarkable RISC processes are realized and TADF features can be expected. Moreover, the large planarity for studied molecules brings small FWHM value with decreased reorganization energies and restricted geometry changes between <em>S₁</em> and ground state (<em>S₀</em>). However, the ΔE_ST values for large planarity molecules are increased and insufficient RISC processes are determined. Thus, the relationship between efficient RISC process with large SOC values and narrowband emission with small FWHM values should be carefully balanced by wise molecular design strategy. This work illustrates the key physical parameters in regulating FWHM values and TADF properties, which could pave the way for the development of efficient MR TADF molecules.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112611"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158616","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}

{"title":"CeO2 nanosheets for high performance aqueous battery systems","authors":"Fenghua Zhu,&nbsp;Haowen Liu","doi":"10.1016/j.chemphys.2025.112609","DOIUrl":"10.1016/j.chemphys.2025.112609","url":null,"abstract":"<div><div>CeO₂ is a promising candidate as electrodes for aqueous battery systems, however, the bulk particles show rapid capacity fading. This work prepares CeO₂ nanosheets via a rapid microwave heating route in 10 min. Benefitting from the unique two-dimensional structure and rich oxygen vacancies, the assembled CeO₂ nanosheets electrode delivers a high initial discharge/charge capacity of 706.1/485.0 mAh g⁻¹ at 120 mA/g, a good reversible capacity of 182.4 mAh g⁻¹ remains after 400 cycles, superior rate capability (91.1 mAh g⁻¹ at 480 mA/g), as well as a fast diffusion kinetics (7.8 × 10⁻¹² cm² S⁻¹) for aqueous Zn-ion batteries (AZIBs). Capacitance fading issue has been greatly addressed compared to the reported bulk particles. Also, it exhibits a high specific capacitance of 436.8 F/g at 1 A/g, a long capacitance retention (98.9 % @ the 2nd cycle) after 5000 cycles at 2.0 A/g, a high energy density of 92.4 Wh kg⁻¹ at a power density of 107 W kg⁻¹ for supercapacitors (SCs).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"592 ","pages":"Article 112609"},"PeriodicalIF":2.0,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158613","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}