CrystEngComm最新文献

{"title":"Preparation and properties of HNS spherical agglomerates with hierarchical structures†","authors":"Xiaoqi Sun, Ya Guo, Fangbao Jiao, Fan Ma, Xiaohui Duan and Hongzhen Li","doi":"10.1039/D5CE00374A","DOIUrl":"https://doi.org/10.1039/D5CE00374A","url":null,"abstract":"<p >Spherical agglomeration is an important method for preparing multi-scale particles, especially large-sized particles. To address the issues of small particle size, irregular morphology, and poor flowability associated with existing HNS, the spherical agglomeration behavior of HNS in DMF-H<small>₂</small>O-DCM and DMF-H<small>₂</small>O-Tol solvent systems was systematically studied. The effects of crystallization temperature, the volume ratio of the bridging liquid to the solute (BSR), the volume ratio of the antisolvent to the solvent, the stirring rate, and other parameters on the agglomeration of HNS were determined. HNS spherical agglomerates with a size ranging from 476.28 μm to 886.12 μm were obtained by optimizing the crystallization parameters. The formation of HNS spherical agglomerates involves four processes: crystallization, phase separation, wetting, and adhesion. The agglomeration mechanism was also explained. A comparison of the flowability and combustion performance of spherical agglomerates and raw HNS crystals revealed that the angles of repose for S-HNS-I, S-HNS-II and raw HNS are 20°, 30° and 35°, respectively, while their pressurization rates are 89.21 kPa s<small>⁻¹</small>, 57.47 kPa s<small>⁻¹</small>, and 36.01 kPa s<small>⁻¹</small>, respectively. Spherical agglomerates exhibit enhanced flowability and excellent combustion performance compared with raw HNS. This study provides guidance for applying the spherical agglomeration method in the field of energetic materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 32","pages":" 5413-5420"},"PeriodicalIF":2.6,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810749","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":"Nonlinear optical potential of engineered sodium d-isoascorbate monohydrate single crystals: a comprehensive characterization study†","authors":"Narmadha S., Muthu Senthil Pandian, Nafis Ahmed, B. Sahaya Infant Lasalle and P. Ramasamy","doi":"10.1039/D5CE00527B","DOIUrl":"https://doi.org/10.1039/D5CE00527B","url":null,"abstract":"<p >Sodium <small>D</small>-isoascorbate monohydrate (NDIAM) single crystals were successfully grown from a customised slow cooling technique, and were found to have excellent structural quality, as confirmed by single crystal X-ray diffraction (SXRD) and powder XRD analyses. The crystals are extremely transparent in the visible to near-infrared region, and have a wide optical bandgap of 4.12 eV which makes them ideal for optical applications that require low signal loss. The dielectric studies, along with theoretical polarizability models, indicate a strong dipolar response, which enhances the nonlinear optical (NLO) interactions. Notably, the crystal shows negative photoconductivity, exhibits thermal stability up to 152 °C, and a high laser damage threshold of 5.2 × 10<small>⁸</small> W cm<small>⁻²</small>, which supports its use in high-power laser environments. NLO studies demonstrated that NDIAM possesses good second harmonic generation (SHG) efficiency, which is 1.85 times greater than the standard KDP crystal. Furthermore, third harmonic generation (THG) analysis shows that NDIAM has a positive refractive index and displays multi-phonon absorption behaviour.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 34","pages":" 5684-5701"},"PeriodicalIF":2.6,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144909491","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":"Insights into the high brightness, color purity, narrowband red-emission and luminous mechanism of Eu-doped CaY2Ge4O12†","authors":"Yingyang Zhao, Shuo Zhao, Huiqi Zhang, Guotao Xiang, Xianju Zhou, Dengfeng Li, Xudong Cui, Yanhao Huang and Feng Wang","doi":"10.1039/D5CE00581G","DOIUrl":"https://doi.org/10.1039/D5CE00581G","url":null,"abstract":"<p >In this study, Eu<small>³⁺</small>-doped CaY<small>₂</small>Ge<small>₄</small>O<small>₁₂</small>, capable of emitting narrow-band red light (full width at half maximum of the strong emission peaks was less than 1.5 nm), was first prepared using the high-temperature solid-phase method at different temperatures. But the sintering temperature does not significantly affect the grain size of CaY<small>₂</small>Ge<small>₄</small>O<small>₁₂</small>:Eu<small>³⁺</small> in this study. Under 395 nm excitation, CaY<small>_{2−<em>x</em>}</small>Ge<small>₄</small>O<small>₁₂</small>:<em>x</em>Eu<small>³⁺</small> exhibited extremely high brightness, color purity exceeding 97%, an average correlated color temperature (CCT) of 2200 K, and quantum yield (QY) close to 100%. The emission intensity at 150 °C remained above 85% of that at 27 °C. The excitation transitions of CaY<small>₂</small>Ge<small>₄</small>O<small>₁₂</small>:Eu<small>³⁺</small> were of two types: one was the 4f–4f upward transition of Eu<small>³⁺</small> caused by narrowband excitation at 288, 299, 320, 363, 386, and 395 nm; the other was the valence band (VB) to conduction band (CB) transition caused by 241 nm excitation. Emissions were observed at 580, 592, 613, 652, and 703 nm. Doping concentration is the main factor affecting the grain size and luminescence intensity of CaY<small>₂</small>Ge<small>₄</small>O<small>₁₂</small>:Eu<small>³⁺</small>. Due to Eu ion doping, the crystal field symmetry decreased, lifting the forbidden transition of <small>⁵</small>D<small>₀</small> → <small>⁷</small>F<small>_j</small> (<em>j</em> = 0, 2, 3, 4). Surprisingly, after the forbidden transition <small>⁵</small>D<small>₀</small> → <small>⁷</small>F<small>₄</small> (703 nm) was lifted, it showed anomalous enhancement (much higher than the typically normally strongest transition, <small>⁵</small>D<small>₀</small> → <small>⁷</small>F<small>₄</small> at 613 nm), greatly increasing the red-light brightness to a level comparable to commercial blue and green light samples. Finally, the luminescence and thermal stability mechanisms of CaY<small>_{2−<em>x</em>}</small>Ge<small>₄</small>O<small>₁₂</small>:<em>x</em>Eu<small>³⁺</small> were detailed.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 32","pages":" 5501-5513"},"PeriodicalIF":2.6,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810717","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":"Effects of chloride and oxygen ions in rutile TiO2 nanorod synthesis by the molten-salt method","authors":"Yangyi Wang, Feifang Zhang, Yijia Li, Xiuliang Hou and Mingqiao Ge","doi":"10.1039/D5CE00582E","DOIUrl":"https://doi.org/10.1039/D5CE00582E","url":null,"abstract":"<p >Rutile TiO<small>₂</small> nanorods have been extensively employed in numerous fields owing to their distinctive morphology, exceptional physical and chemical properties, and biocompatibility. A considerable number of researchers have reported the synthesis method of molten salt for high-aspect-ratio rutile TiO<small>₂</small> nanorods. Nevertheless, their crystal phase and crystal growth mechanism remain enigmatic. In this investigation, rutile TiO<small>₂</small> nanorods were synthesized from anatase TiO<small>₂</small>, potassium chloride, and potassium carbonate at 1173 K. The effects of Cl<small>⁻</small> and O<small>²⁻</small> on the crystal transformation and growth were further meticulously investigated by integrating experimental results, morphological prediction, and relevant adsorption energy calculation data. It was discovered that Cl<small>⁻</small> could facilitate the crystal phase transformation from anatase TiO<small>₂</small> to rutile TiO<small>₂</small>. The ratio of Cl<small>⁻</small> to anatase TiO<small>₂</small> ranging from 5.8 : 12 to 9.2 : 12 is beneficial to forming rutile TiO<small>₂</small> nanorods. But, a portion of blocky rutile TiO<small>₂</small> still exists in the final product. Moreover, O<small>²⁻</small> is conducive to forming potassium titanate (K<small>₂</small>Ti<small>_<em>x</em></small>O<small>_{2<em>x</em>+1}</small>) nanorods, which inhibit the conversion of anatase TiO<small>₂</small> to rutile TiO<small>₂</small>. The combination of Cl<small>⁻</small> and O<small>²⁻</small> under the conditions of precisely controlling the molar ratio of Cl<small>⁻</small>/O<small>²⁻</small> within 4.14 to 9.20 is conducive to the synthesis of rutile TiO<small>₂</small> nanorods. The results provide a good reference for precisely controlling the synthesis of rutile TiO<small>₂</small> nanorods to achieve the desired properties.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 31","pages":" 5327-5336"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144773351","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":"Halogen-driven modulation of iridium-functionalized zirconium-based metal–organic frameworks for electrocatalytic oxygen evolution in acidic media†","authors":"Yu-Chi Wang, Shang-Cheng Yang, Cheng-Hui Shen, Tzu-Hsien Yang and Chung-Wei Kung","doi":"10.1039/D5CE00543D","DOIUrl":"https://doi.org/10.1039/D5CE00543D","url":null,"abstract":"<p >Nanocrystals of a zirconium-based metal–organic framework (MOF), UiO-66, and its derivatives constructed from three distinct halogen-functionalized linkers, are synthesized. They are further subjected to post-synthetic modification to immobilize redox-active iridium ions on their nodes, where missing-linker defects are located. The crystallinity, morphology and porosity of all MOFs before and after functionalizing iridium are characterized. The number of defects in each MOF and the loading of iridium in each iridium-functionalized MOF are also quantified. Electrochemical behaviours of all iridium-functionalized MOFs and their corresponding redox-based charge-hopping processes occurring between immobilized iridium sites in the frameworks are investigated. All iridium-functionalized MOFs are employed as electrocatalysts for the oxygen evolution reaction (OER) in an acidic aqueous electrolyte containing 0.1 M of HClO<small>₄</small>, where Zr-based MOFs are chemically robust. Impedance experiments and further distribution of relaxation times (DRT) analysis suggest that all halogen-functionalized linkers can facilitate the OER kinetics occurring on the neighbouring iridium sites immobilized in MOFs, while the MOF with heavy iodo groups on its linkers strongly retards the mass transfer during the OER. With both facile mass transfer and fast catalytic kinetics, both iridium-functionalized MOFs with chloro and bromo groups on their linkers thus exhibit better electrocatalytic activity for the OER compared to their counterparts without halogen atoms and with iodo groups. The iridium-functionalized MOF with chloro groups can achieve 1 mA cm<small>⁻²</small> for the OER at an overpotential of 327 mV, outperforming that required by the iridium-functionalized UiO-66 (383 mV). Findings here highlight the importance of modulating the chemical functionality of linkers in stable MOFs in order to boost the electrocatalytic activity of the frameworks.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 35","pages":" 5830-5840"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007863","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":"Ruthenium-modified oxygen-deficient NiCoP catalysts for efficient electrocatalytic water splitting†","authors":"Bo-yao Zhang, Song-lin Xu, Jia Li, Xin-Xin Zhao, Rong-da Zhao, Ming-chang Zhang, De-peng Zhao and Lihua Miao","doi":"10.1039/D5CE00510H","DOIUrl":"https://doi.org/10.1039/D5CE00510H","url":null,"abstract":"<p >Ruthenium-doped nickel cobalt compounds are promising catalysts for the hydrogen evolution reaction. We report a synergistic strategy of “defect engineering + noble metal modification” to develop Ru-modified oxygen-deficient NiCoP catalysts (Ru-NiCoP-O<small>_v</small>). By precisely controlling the synthesis conditions, we systematically investigated the impact of Ru modification and oxygen vacancies on the electrocatalytic performance of NiCoP catalysts. The prepared Ru-NiCoP-O<small>_v</small> catalyst exhibits excellent hydrogen evolution catalytic performance in conventional alkaline electrolyte (1 M KOH): it requires only a low overpotential of 51.5 mV at a current density of −10 mA cm<small>⁻²</small> for the hydrogen evolution reaction (HER). More importantly, the catalyst also performs excellently in simulated seawater electrolysis environments (1 M KOH seawater solution), with an HER overpotential of 68.1 mV at −10 mA cm<small>⁻²</small> current density. This outstanding performance fully demonstrates the importance of the synergistic effect of Ru modification and oxygen vacancies in enhancing catalytic activity, providing new design strategies and experimental evidence for developing efficient seawater electrolysis catalysts, and offering a feasible approach to achieving efficient and low-cost hydrogen energy production.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 32","pages":" 5485-5500"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810716","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":"Synthesis and characterization of TiP-doped diamond in the FeNi–C system under HTHP conditions","authors":"Bowei Li, Ziqi Wang, Zhiwen Wang, Yang Liu, Hongyu Zhao, Qianyu Guo, Aokai Xu, Hongan Ma and Xiaopeng Jia","doi":"10.1039/D5CE00609K","DOIUrl":"https://doi.org/10.1039/D5CE00609K","url":null,"abstract":"<p >In this paper, phosphorus-doped diamond with n-type semiconductor properties was successfully synthesized by adding TiP to the FeNi–C system using a large-volume cubic high pressure apparatus (CHPA) at 6 GPa and 1430–1510 °C. The morphology, crystallinity, internal content, internal atomic bonding and electrical properties of the samples were studied and characterized in detail. With the increase of TiP addition, the crystal color becomes lighter, the surface defects increase, the crystal quality deteriorates, the internal stress increases, and the nitrogen content of the crystals decreases. This means that the addition of TiP not only reduces the number of nitrogen atoms entering the diamond, but also has a negative effect on the crystal quality of diamond. The addition of TiP allows phosphorus atoms to enter the diamond lattice and bond with carbon atoms, and gives the crystals n-type conductivity. The electrical conductivity is enhanced with the increase of TiP addition. TiP was used as an additive to successfully synthesize diamond with n-type semiconductor properties in the FeNi–C system. The addition of TiP not only reduces the effect of nitrogen in the system on phosphorus doping, but also has the advantages of easier access to the synthesis system and reduced impurities as a phosphide. In this paper, the possibility of TiP as a phosphorus source for the synthesis of phosphorus-doped diamond is verified, which provides valuable data for the synthesis of n-type semiconductor diamond by HPHT.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 33","pages":" 5644-5651"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144868548","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":"Anisotropic mechanical response and aliovalent doping-induced strengthening in CaF2 single crystals: a combined experimental and first-principles study","authors":"Yeqi Zhuo, Shukuan Guo, Bo Zhang, Zhen Zhang, Dapeng Jiang, Junyang Liu, Lizhi Fang, Huamin Kou and Liangbi Su","doi":"10.1039/D5CE00508F","DOIUrl":"https://doi.org/10.1039/D5CE00508F","url":null,"abstract":"<p >CaF<small>₂</small> single crystals, despite their excellent optical properties, are limited in extreme environments by intrinsic brittleness and low mechanical strength. In this study, we investigate the anisotropic mechanical behavior and strengthening mechanisms of pure and Y<small>³⁺</small>-doped CaF<small>₂</small> crystals. Nanoindentation and uniaxial compression tests reveal significant mechanical anisotropy: the &lt;100&gt; orientation exhibits the highest Young's modulus, compressive strength, and Vickers hardness, followed by the &lt;110&gt; and &lt;111&gt; orientations. This trend contrasts sharply with conventional face-centered cubic metals and covalent semiconductors. Importantly, Y<small>³⁺</small> doping further elevates these properties. Notably, doping with about 1 at% Y<small>³⁺</small> increases the compressive strength along the &lt;111&gt; direction by 94%, from 101 MPa to 196 MPa. We attribute the mechanical anisotropy to variations in Coulomb interactions between like-charged ions during compression along different crystallographic directions. The strengthening effect of Y<small>³⁺</small> doping is explained by lattice distortion and enhanced Y–F bond strength compared to native Ca–F bonds. These findings provide valuable insights for understanding and designing optical devices for extreme conditions.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 32","pages":" 5449-5458"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810753","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":"Transformation of carbon dioxide catalyzed using an N-heterocyclic carbene copper(i)-embedded metal–organic framework†","authors":"Li-Xin You, Xin-Yu Wang, Jin-Rong Li, Jie Guo, Gang Xiong, Fu ding and Ya-Guang Sun","doi":"10.1039/D5CE00627A","DOIUrl":"https://doi.org/10.1039/D5CE00627A","url":null,"abstract":"<p >Transformation of carbon dioxide (CO<small>₂</small>) into high-value chemicals has attracted increasing attention because CO<small>₂</small> is an abundant, inexpensive and non-toxic renewable carbon resource. Herein, a novel three-dimensional metal–organic framework, namely, {[Zn<small>₄</small>(μ<small>₄</small>-O)(<small>L</small>)<small>₄</small>·4(H<small>₂</small>O)]·2(NO<small>₃</small>)}<small>_<em>n</em></small> (Zn-MOF), was synthesized under hydrothermal conditions using an azolium-based ligand, 1,3-bis(4-carboxybenzyl)-4-methyl-1<em>H</em> imidazolium chloride (H<small>₂</small>L<small>⁺</small>Cl<small>⁻</small>). Subsequently, Cu(<small>I</small>)-NHC@Zn-MOF was prepared by introducing N-heterocyclic carbine-Cu(<small>I</small>) active sites into the Zn-MOF using a post-synthesis modification (PSM) method, and it was characterized through powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Cu(<small>I</small>)-NHC@Zn-MOF was successfully employed as a highly efficient catalyst for the C–H activated carboxylation of terminal alkynes with CO<small>₂</small> (1 atm) under mild conditions, achieving an isolated yield of up to 98%. The catalyst exhibited excellent recyclability and maintained high activity over three consecutive cycles without losing its structural integrity. Additionally, the role of Cu(<small>I</small>)-NHC@Zn-MOF and the reaction mechanism were comprehensively discussed.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 33","pages":" 5625-5632"},"PeriodicalIF":2.6,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144868565","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":"Cross-correlated experimental and theoretical characterisation of orpiment As2S3, a potential material for new advanced technological applications†","authors":"Gianfranco Ulian, Francesca Ranellucci and Giovanni Valdrè","doi":"10.1039/D5CE00525F","DOIUrl":"https://doi.org/10.1039/D5CE00525F","url":null,"abstract":"<p >In the ever-growing search for new materials in optical, electronic and photovoltaic applications, chalcogenides, such as amorphous diarsenic trisulfide (As<small>₂</small>S<small>₃</small>), are being deeply investigated. However, very few and incomplete data are available on crystalline As<small>₂</small>S<small>₃</small> (space group <em>P</em>2<small>₁</small>/<em>n</em>), known as mineral orpiment. In the present work, several experimental techniques were employed to analyse the crystal structure, morphology, chemical composition and vibrational properties of the bulk and mechanically cleaved (010) orpiment surface. Also, cross-correlated atomic-scale <em>ab initio</em> simulations corroborated and explained the new experimental data. Orpiment showed a semiconducting behaviour, with an indirect band gap of 2.44 eV and an optical <em>Γ</em>–<em>Γ</em> gap of 2.63 eV, which agrees with previous optical-absorption edge measurements. Furthermore, the complete stiffness tensor and the phonon band structure were reported for the first time. All these quantities are of utmost importance for devising new possible applications of crystalline orpiment in the technological and materials science fields.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 30","pages":" 5126-5139"},"PeriodicalIF":2.6,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00525f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144714643","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}