Chemical Physics最新文献

{"title":"Investigating weak dipole interactions of cyclic nitriles in the gas phase: Theoretical views on molecular stability and reactivity","authors":"Giridhar Baburao, Pranab Chandra Kayal, Gopi Ragupathy","doi":"10.1016/j.chemphys.2025.112831","DOIUrl":"10.1016/j.chemphys.2025.112831","url":null,"abstract":"<div><div>We investigated hydrogen bonding interactions between cyclic nitriles (C<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>CN, C<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>CN, C<span><math><msub><mrow></mrow><mrow><mn>5</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>5</mn></mrow></msub></math></span>CN, C<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>5</mn></mrow></msub></math></span>CN, C<sub>10</sub>H<span><math><msub><mrow></mrow><mrow><mn>7</mn></mrow></msub></math></span>CN) and Lewis acids/bases (H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>O, HCl, HCN, NH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>, and C<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>), identifying N<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>H<span><math><mo>−</mo></math></span>O, N<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>H<span><math><mo>−</mo></math></span>Cl, N<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>H<span><math><mo>−</mo></math></span>C, and N<span><math><mrow><mo>⋯</mo><mspace></mspace></mrow></math></span>H<span><math><mo>−</mo></math></span>N bonds, with nitriles acting as proton acceptors. Among the proton donors, HCl exhibited the strongest interactions due to its highly acidic proton. The bimolecular complexes formed with C<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>CN, C<span><math><msub><mrow></mrow><mrow><mn>4</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>CN, and C<span><math><msub><mrow></mrow><mrow><mn>5</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>5</mn></mrow></msub></math></span>CN showed enhanced stability, attributed to enhanced electronic effects. Notably, the nitrile molecules examined in this study also possess astrochemical significance, as they have recently been detected in the interstellar medium. A comprehensive analysis of geometrical parameters, interaction energies, vibrational frequency shifts, hyperconjugation, and electron density offered deeper insights into the nature of these interactions and the resulting structural changes. We performed Atoms in Molecules (AIM) analysis to determine electron densities [<span><math><mrow><mi>ρ</mi><mrow><mo>(</mo><msub><mrow><mi>r</mi></mrow><mrow><mi>c</mi></mrow></msub><mo>)</mo></mrow></mrow></math></span>] and the Laplacian of electron density [<span><math><mro","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112831"},"PeriodicalIF":2.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663521","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":"Tuning the properties of SrI2: A DFT study on the contributions of S and Se doping","authors":"Hafeez Ur Rehman ,&nbsp;Zahid Usman ,&nbsp;M. Usman Abdullah ,&nbsp;Ahmad Usman","doi":"10.1016/j.chemphys.2025.112841","DOIUrl":"10.1016/j.chemphys.2025.112841","url":null,"abstract":"<div><div>Strontium iodide (SrI₂) and S and Se doped variants of it were systematically investigated with the help of density functional theory (DFT), as it was implemented in WIEN2k using GGA-PBE approximation. Supercell of size 2 × 1 × 1 was adopted, which relates to the doping level of 12.5 %. The study targeted such properties as structural, electronic, optical, mechanical, and thermoelectric properties. Electronic band analysis identified direct band gap properties for pure and doped SrI₂, with the respective modified band gap values providing a take on doping in the electronic performance. The total density of states (TDOS) and partial density of states (PDOS) gave more understanding on the electronic behavior. Static refractive index of doped system has been increased up to 2.59 with respect to 2.25 of pristine SrI₂ by optical analysis. Bulk modulus, shear modulus, Young's modulus, B/G ratio as well as Poisson's ratio for mechanical characteristics were measured in order to determine the ductility and stiffness. At the 200–800 K range the thermoelectric calculations indicated an enhanced electrical conductivity and power factor in both S-doped and Se-doped SrI₂, which may have applications in energy.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112841"},"PeriodicalIF":2.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144634114","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":"Layer dependent optical properties of γ-graphyne","authors":"Sajid Ali ,&nbsp;Basit Ali ,&nbsp;Sani Abdulkarim ,&nbsp;Mengtao Sun","doi":"10.1016/j.chemphys.2025.112847","DOIUrl":"10.1016/j.chemphys.2025.112847","url":null,"abstract":"<div><div>Stacking two-dimensional (2D) materials vertically provides a distinct platform for creating hybrid materials with adjustable properties. Based on this research study, density functional theory (DFT) was complemented by including van der Waals density function, where γ-graphyne and stacking structures (monolayer, bilayer, tri-layer and bulk forms) were systematically considered. According to our findings, AB stacking is more stable than AA-stacking, with an electrical bandgap that changes depending on the stacking configuration. We found a new two-dimensional (2D) carbon allotrope based on the AB-stacked configuration, which goes beyond conventional van der Waals (vdW) homogeneous stacking. The AB-stacked configuration represents a structurally optimized arrangement with distinct electronic characteristics compared to other stacking forms. Interestingly, tri-layer γ-graphyne can also be used to create various 2D carbon allotropes with unique carbon networks. We observed that bulk γ-graphyne exhibits either semiconductor or metallic behavior, depending on the stacking arrangement. Additionally, the interlayer vdW interactions cause a redshift in the optical absorption peaks for bulk γ-graphyne compared to the monolayer, with notable differences in the spectra for various stacking configurations below 1 eV. These results highlight few-layer γ-graphyne's encouraging potential for developing carbon-based nanoelectronics. Additionally, this introduces a novel approach for designing new two-dimensional carbon allotropes by vertically stacking graphyne with acetylene linkages.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112847"},"PeriodicalIF":2.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144569741","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":"Structural stability and electronic properties of fluorine-doped graphene","authors":"Lukman Olatomiwa Agbolade ,&nbsp;Abdullah Chik ,&nbsp;Tijjani Adam ,&nbsp;Mohd Fairus Ahmad ,&nbsp;Abdelkader Kara","doi":"10.1016/j.chemphys.2025.112827","DOIUrl":"10.1016/j.chemphys.2025.112827","url":null,"abstract":"<div><div>In this work, we employed density functional theory (DFT) within the generalized gradient approximation (GGA) to investigate the structural and electronic modifications of functionalized graphene induced by different levels of fluorination. Our results reveal significant geometric reconstructions, including localized lattice deformations resulting in the loss of planarity. We also found fluorine to act as an electron acceptor, forming a polar covalent bond. Lastly, the Bader charge analysis and Density of States (DOS) highlight redistribution and configuration-dependent electronic transitions near the Fermi level. These findings reveal how fluorination patterns tune graphene's electronic properties, providing potential for various applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112827"},"PeriodicalIF":2.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144587572","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":"Electronic transitions of the purpurin dye. UV–vis polarization spectroscopy and quantum chemical predictions","authors":"Duy Duc Nguyen ,&nbsp;Nykola C. Jones ,&nbsp;Søren V. Hoffmann ,&nbsp;Jens Spanget-Larsen","doi":"10.1016/j.chemphys.2025.112848","DOIUrl":"10.1016/j.chemphys.2025.112848","url":null,"abstract":"<div><div>Purpurin (1,2,4-trihydroxy-9,10-anthraquinone) is investigated by Synchrotron Radiation Linear Dichroism (SRLD) spectroscopy using stretched polyethylene as an anisotropic solvent, covering the range 58,000–15,000 cm⁻¹ (172–670 nm). The observed wavenumbers, intensities, and polarization directions are compared with theoretical predictions using Time-Dependent Density Functional Theory (TD–DFT), leading to assignment and characterization of all major spectral features in the investigated region. The results demonstrate that the spectrum of purpurin is closely related to that of quinizarin (1,4-dihydroxy-9,10-anthraquinone), indicating that the additional hydroxy group in the 2-position in purpurin can be considered as a minor perturbation of the chromophore.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112848"},"PeriodicalIF":2.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144580992","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 investigation of electronic structure, optical, mechanical properties, and strain effects of double perovskite Cs2LiSbX6(X = Cl, Br, I)","authors":"Zesheng Gui ,&nbsp;Jinxue Cui ,&nbsp;Hao Zhou ,&nbsp;Tianji Ou ,&nbsp;Jiaqi Yu ,&nbsp;Shuang Feng ,&nbsp;Chunzhi Li ,&nbsp;Peifang Li ,&nbsp;Xinjun Ma ,&nbsp;Chunxiao Gao","doi":"10.1016/j.chemphys.2025.112846","DOIUrl":"10.1016/j.chemphys.2025.112846","url":null,"abstract":"<div><div>We conducted an in-depth investigation on the lattice structure, optoelectronic properties, and elastic constants of halide double perovskite Cs₂LiSbX₆ (X = Cl, Br, I) based on first principles calculations. The computed elastic and mechanical properties demonstrate that all three materials exhibit mechanical stability, alongside excellent ductility and anisotropic behavior. In addition, these three materials Cs₂LiSbCl₆, Cs₂LiSbBr₆, and Cs₂LiSbI₆ exhibit indirect band gaps of 3.65 eV, 3.05 eV and 2.29 V, respectively, and are classified as wide bandgap materials. The optical characteristics of Cs₂LiSbX₆ were evaluated through the computation of several key parameters: the real component of the dielectric function (ε₁(ω)), the imaginary component of the dielectric function (ε₂(ω)), the refractive index (n(ω)), and the absorption coefficient (α(ω)). In addition, the strain engineering, spanning from −6 % to 6 %, reveals that compressive strain(tensile strain) narrows(widens) the bandgap, leading to a blueshift(redshift) in the absorption edge. These findings provide theoretical support for adjusting the bandgaps of Cs₂LiSbX₆ perovskites.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112846"},"PeriodicalIF":2.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144569740","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":"Z-scheme WSTe/MoSSe van der Waals heterojunction as a hydrogen evolution photocatalyst: First-principles predictions","authors":"Lei Tian ,&nbsp;Jiahuan Hu ,&nbsp;Zhenyi Jiang ,&nbsp;Xuanhong Wang","doi":"10.1016/j.chemphys.2025.112842","DOIUrl":"10.1016/j.chemphys.2025.112842","url":null,"abstract":"<div><div>WSTe/MoSSe heterojunction is constructed, covering four contact modes. The calculated built-in electric field (E_IF) and interlayer spacing (h) validate the van der Waals (vdWs) heterojunction formation. In the analysis of interfacial charge behavior, the electrostatic interaction of Janus material heterojunction significantly affects charge transfer. Systematic analysis of density of states (DOS) and band structure reveals that all four contact configurations form type-II heterojunctions. By calculating conduction band offset (CBO) and valence band offset (VBO), it is found that the heterostructure in S<img>se contact mode is more favorable to hydrogen evolution, the analysis of differential charge density and band alignment further confirms the <em>Z</em>-scheme charge transfer mechanism in the heterojunction material system. Further investigations reveal 0.5 eV and 1.0 eV overpotentials for reduction and oxidation processes, respectively. The introduction of U_e (0.5 V) lowers the Gibbs free energy in the WSTe/MoSSe heterojunction system, demonstrating its spontaneous water-splitting capability under light exposure. Thermodynamic driving force enables autonomous photocatalysis, enhancing hydrogen production efficiency and positioning the material for solar energy conversion</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112842"},"PeriodicalIF":2.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144556577","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":"Electronic and optical properties modulation of heterostructures based on Na2S and h-BN under biaxial strain","authors":"Xiaotian Yang ,&nbsp;Hang Xu ,&nbsp;Jiping Hu ,&nbsp;Jun Zhang ,&nbsp;Shipei Ji ,&nbsp;Yipu Qu ,&nbsp;Juin J. Liou ,&nbsp;Fang Wang ,&nbsp;Yuhuai Liu","doi":"10.1016/j.chemphys.2025.112835","DOIUrl":"10.1016/j.chemphys.2025.112835","url":null,"abstract":"<div><div>This research explores the structural, electronic, and optical characteristics of Na₂S monolayers and bilayers, as well as their heterostructures with h-BN, using first-principles calculations. The results reveal that the heterostructure of Na₂S monolayers and h-BN effectively modulates the bandgap while maintaining the intrinsic band structure trend of Na₂S. The introduction of heterostructures and misaligned stacking with h-BN leads to a blue shift in optical spectra, potentially eliminating visible light absorption under extreme conditions. Additionally, h-BN significantly stabilizes light absorption and reflection within the visible range, maintaining a consistent trend. Strain engineering further adjusts the sandwiched heterostructure's bandgap, achieving a total bandgap variation of ∼0.6 eV under −6 % to +6 % strain and exhibiting Type-I → II → I band alignment transitions. These findings offer insights for designing optoelectronic devices and provide theoretical guidance for applications like optical switches, integrated filters, and memristor substrates in different environments.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112835"},"PeriodicalIF":2.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535206","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":"Hydrogen production from photocatalytic water splitting in the InP/SnS2 heterojunction: First-principles calculations","authors":"Dan Li ,&nbsp;Wentao Luo ,&nbsp;Xing Wei ,&nbsp;Yan Zhang ,&nbsp;Yun Yang ,&nbsp;Jian Liu ,&nbsp;Ye Tian ,&nbsp;Li Duan","doi":"10.1016/j.chemphys.2025.112840","DOIUrl":"10.1016/j.chemphys.2025.112840","url":null,"abstract":"<div><div>In the present era, the environmental issues and resource shortages caused by energy development have become increasingly severe. To address this problem, the method of preparing hydrogen through photocatalytic water splitting technology has been proposed and has developed rapidly. This study investigates InP/SnS₂ heterojunctions for photocatalytic water splitting using first-principles calculations. The heterojunction has a 1.33 eV bandgap with a Type-II alignment, facilitating effective electron-hole separation. Work function analysis shows electrons transfer from InP to SnS₂, with a total Bader charge transfer of 0.10 <span><math><mfenced><mi>e</mi></mfenced></math></span>. The charge transfer follows a <em>Z</em>-scheme pathway, enhancing photocatalytic activity. The heterojunction meets redox requirements, exhibits an absorption peak at 2.07 × 10⁵ cm⁻¹ within the visible spectrum, and achieves a solar-to‑hydrogen efficiency of 9.83 %. These properties suggest that InP/SnS₂ heterojunctions are promising for future photocatalytic applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112840"},"PeriodicalIF":2.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144572554","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":"Ultraviolet photodissociation spectroscopy of protonated adenosine and its hydrogen-bonded clusters with amino acid enantiomers","authors":"Riyo Nakanishi,&nbsp;Akimasa Fujihara","doi":"10.1016/j.chemphys.2025.112837","DOIUrl":"10.1016/j.chemphys.2025.112837","url":null,"abstract":"<div><div>The effects of hydrogen bonding on the photochemical properties of nucleosides were investigated using ultraviolet photodissociation spectroscopy at 8 K in the gas phase. Photoinduced glycosidic bond cleavage of protonated adenosine is inhibited by hydrogen bonding with histidine. In the spectrum of protonated adenosine, a distinct band at 288 nm and broad bands were observed. The broad bands were similar to those of protonated adenosine hydrogen-bonded to <span>d</span>-histidine. In the spectrum of protonated adenosine hydrogen-bonded with <span>l</span>-histidine, the relative intensity increased gradually with increasing excitation energy, with the absorption onset at 285 nm. The protonation sites of protonated adenosine and its hydrogen-bonded cluster with <span>d</span>-histidine were located at the N3 position of the adenine moiety. The protonation site of protonated adenosine hydrogen-bonded with <span>l</span>-histidine was N1. The S₁–S₀ transition of N3-protonated adenosine was red-shifted compared to that of N1-protonated adenosine. Adenosine recognizes enantiomers through protonation and its electronic structure.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"598 ","pages":"Article 112837"},"PeriodicalIF":2.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144549211","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}