A series of novel MIL-53(Fe)/CoWO4 composites were synthesized by combining MIL-53(Fe) and CoWO4 nanoparticles via solvothermal method. The structural characterizations showed that CoWO4 nanoparticles were uniformly distributed on the surface of hexagonal bipyramid MIL-53(Fe). Combining XPS and Mott-Schottky plots, a Z-scheme heterojunction was formed between MIL-53(Fe) and CoWO4, resulting in a significant improvement in the electron-hole pair separation efficiency. UV–vis diffused reflectance spectra indicated that the optical arrange of MIL-53(Fe)/CoWO4 composites were expanded to visible light. The photocatalytic degradation experiments under visible light irradiation showed that MIL/CWO-60 synergistically with PMS degraded 90.5 % of TC-HCl within 50 min. The XRD spectra of used and unused composites were identical, indicating good stability in four consecutive cycles. Electron paramagnetic resonance (EPR) and free radicals trapping experiment revealed that active species included O2−, SO4−, h+, OH and 1O2, and mechanism of the synergistic degradation of TC-HCl by MIL-53(Fe)/CoWO4 composites and PMS was proposed.
{"title":"Synergistic photocatalytic degradation of TC-HCl by MIL-53(Fe)/CoWO4 composite and PMS under visible light","authors":"Qian Liu , Panpan Xu , Qianqian Zhang, Guangming Han, Ling Li, Limin Zhou","doi":"10.1016/j.chemphys.2024.112479","DOIUrl":"10.1016/j.chemphys.2024.112479","url":null,"abstract":"<div><div>A series of novel MIL-53(Fe)/CoWO<sub>4</sub> composites were synthesized by combining MIL-53(Fe) and CoWO<sub>4</sub> nanoparticles via solvothermal method. The structural characterizations showed that CoWO<sub>4</sub> nanoparticles were uniformly distributed on the surface of hexagonal bipyramid MIL-53(Fe). Combining XPS and Mott-Schottky plots, a Z-scheme heterojunction was formed between MIL-53(Fe) and CoWO<sub>4</sub>, resulting in a significant improvement in the electron-hole pair separation efficiency. UV–vis diffused reflectance spectra indicated that the optical arrange of MIL-53(Fe)/CoWO<sub>4</sub> composites were expanded to visible light. The photocatalytic degradation experiments under visible light irradiation showed that MIL/CWO-60 synergistically with PMS degraded 90.5 % of TC-HCl within 50 min. The XRD spectra of used and unused composites were identical, indicating good stability in four consecutive cycles. Electron paramagnetic resonance (EPR) and free radicals trapping experiment revealed that active species included <img>O<sup>2−</sup>, SO<sub>4</sub><sup><img>−</sup>, h<sup>+</sup>, <img>OH and <sup>1</sup>O<sub>2</sub>, and mechanism of the synergistic degradation of TC-HCl by MIL-53(Fe)/CoWO<sub>4</sub> composites and PMS was proposed.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112479"},"PeriodicalIF":2.0,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442250","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}
Pub Date : 2024-10-11DOI: 10.1016/j.chemphys.2024.112488
Qianqian Zeng , Xi Liu , Lei Wang , Shuangcui Li , Xiaoyin Xie , Guanchen Liu , Zhihai Liu
We used work-function-tuned poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the electron-transport layer for wide-bandgap (1.74 eV) perovskite solar cells (PSCs). With the coating of polyethylenimine, the work function of PEDOT:PSS was modified from −5.03 to −4.05 eV, which enabled efficient electron transportation from perovskite absorber to cathode. With this technique, the standard-structured n-i-p PSCs showed an average power-conversion-efficiency (PCE) of 18.6 %, which is higher than that (17.5 %) of inverted PSCs with PEDOT:PSS as the hole-transport layer. Moreover, the long-term stability of the PSCs was enhanced with the PCE degradation significantly suppressed from 29.7 % to 15.6 % after a 10 days’ measurement in ambient.
{"title":"High-performance wide-bandgap perovskite solar cells using poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) as the electron-transport layer","authors":"Qianqian Zeng , Xi Liu , Lei Wang , Shuangcui Li , Xiaoyin Xie , Guanchen Liu , Zhihai Liu","doi":"10.1016/j.chemphys.2024.112488","DOIUrl":"10.1016/j.chemphys.2024.112488","url":null,"abstract":"<div><div>We used work-function-tuned poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the electron-transport layer for wide-bandgap (1.74 eV) perovskite solar cells (PSCs). With the coating of polyethylenimine, the work function of PEDOT:PSS was modified from −5.03 to −4.05 eV, which enabled efficient electron transportation from perovskite absorber to cathode. With this technique, the standard-structured <em>n</em>-i-p PSCs showed an average power-conversion-efficiency (PCE) of 18.6 %, which is higher than that (17.5 %) of inverted PSCs with PEDOT:PSS as the hole-transport layer. Moreover, the long-term stability of the PSCs was enhanced with the PCE degradation significantly suppressed from 29.7 % to 15.6 % after a 10 days’ measurement in ambient.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112488"},"PeriodicalIF":2.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142432762","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}
Pub Date : 2024-10-11DOI: 10.1016/j.chemphys.2024.112474
Maryam Fatima , Bandar Almohsen , S. Iqbal , Youming Lei , Alessandro Nutini
Nanomaterials are revolutionizing tissue engineering by significantly enhancing enzyme-mediated chemical processes and cellular activities, thereby advancing the development of more effective therapeutic strategies. This research delves into the intricate dynamics of enzyme diffusion within tissue matrices, providing a comprehensive computational modeling framework aimed at optimizing enzyme concentration control in tissue scaffolds. Through advanced numerical algorithms and computational analysis, the study simulates optimal control strategies for regulating nanozyme levels, ensuring precise and sustained enzymatic activity within the scaffolds. A novel aspect of this work is the integration of videographic records, which offers an enriched understanding of the complex interactions between nanomaterials and biological tissues, providing detailed insights into the system’s operational dynamics. The study bridges the gap between experimental methodologies and theoretical models, aligning with the cutting-edge research in chemical physics and physical chemistry by offering novel approaches to tissue engineering challenges. The findings underscore the critical role of nanomaterials in achieving precise enzymatic control, which is pivotal for the development of advanced biomimetic systems and improved therapeutic outcomes. This work contributes to the ongoing frontier research in physical phenomena within chemistry, biology, and materials science, by providing significant new insights into enzyme delivery mechanisms and their application in biomedical contexts. The research not only highlights the importance of innovative methodologies in tissue engineering but also sets the stage for future experimental validations and potential clinical applications
{"title":"Nanozyme-enhanced enzyme control: Computational strategies for precise and sustained enzymatic activity in tissue engineering","authors":"Maryam Fatima , Bandar Almohsen , S. Iqbal , Youming Lei , Alessandro Nutini","doi":"10.1016/j.chemphys.2024.112474","DOIUrl":"10.1016/j.chemphys.2024.112474","url":null,"abstract":"<div><div>Nanomaterials are revolutionizing tissue engineering by significantly enhancing enzyme-mediated chemical processes and cellular activities, thereby advancing the development of more effective therapeutic strategies. This research delves into the intricate dynamics of enzyme diffusion within tissue matrices, providing a comprehensive computational modeling framework aimed at optimizing enzyme concentration control in tissue scaffolds. Through advanced numerical algorithms and computational analysis, the study simulates optimal control strategies for regulating nanozyme levels, ensuring precise and sustained enzymatic activity within the scaffolds. A novel aspect of this work is the integration of videographic records, which offers an enriched understanding of the complex interactions between nanomaterials and biological tissues, providing detailed insights into the system’s operational dynamics. The study bridges the gap between experimental methodologies and theoretical models, aligning with the cutting-edge research in chemical physics and physical chemistry by offering novel approaches to tissue engineering challenges. The findings underscore the critical role of nanomaterials in achieving precise enzymatic control, which is pivotal for the development of advanced biomimetic systems and improved therapeutic outcomes. This work contributes to the ongoing frontier research in physical phenomena within chemistry, biology, and materials science, by providing significant new insights into enzyme delivery mechanisms and their application in biomedical contexts. The research not only highlights the importance of innovative methodologies in tissue engineering but also sets the stage for future experimental validations and potential clinical applications</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112474"},"PeriodicalIF":2.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529805","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}
Pub Date : 2024-10-11DOI: 10.1016/j.chemphys.2024.112491
Salman Ahmad , Amin-ur-Rehman , Sikandar Azam , Muhammad Asif Hasham , Maida Jameel , Abdulraheem SA Almalki
We studied the electronic and optical properties of pure and Eu-doped CdSe phosphor materials using the first-principles calculation method, which is a feature of Density Functional Theory. The FP-LAPW method was employed for the study as incorporated in the Wien2k code. The GGA + U + SOC method of DFT was used for the first time in our study to investigate the electronic as well as optical characteristics of Eu-doped CdSe materials. Eu doping was done in two different ratios to study the effects of altered dopant concentration. The doping increased the band gap of the pure CdSe parental material. The calculated band gaps in our study were 0.42 eV for pure CdSe, 0.67 eV for a single Eu atom doped in CdSe, and 1.64 eV for two Eu atoms doped in CdSe. The measured electronic and optical characteristics of undoped i.e, pure CdSe and Eu-doped CdSe showed that the doping significantly changed the optical behavior of CdSe, which may be useful for applications in phosphor-converted LEDs.
我们利用密度泛函理论的第一性原理计算方法研究了纯 CdSe 和掺 Eu CdSe 荧光材料的电子和光学特性。研究采用了 Wien2k 代码中的 FP-LAPW 方法。在我们的研究中，首次使用了 DFT 的 GGA + U + SOC 方法来研究掺杂 Eu 的 CdSe 材料的电子和光学特性。为了研究掺杂浓度变化的影响，我们以两种不同的比例掺杂了 Eu。掺杂增加了纯 CdSe 母体材料的带隙。在我们的研究中，纯 CdSe 的计算带隙为 0.42 eV，在 CdSe 中掺入单个 Eu 原子的计算带隙为 0.67 eV，在 CdSe 中掺入两个 Eu 原子的计算带隙为 1.64 eV。对未掺杂（即纯 CdSe）和掺杂 Eu 的 CdSe 的电子和光学特性的测量结果表明，掺杂显著改变了 CdSe 的光学行为，这可能有助于荧光粉转换 LED 的应用。
{"title":"Studying the optical and electronic properties of Eu-doped CdSe phosphors using first principles calculations incorporating the spin orbit coupling method of DFT","authors":"Salman Ahmad , Amin-ur-Rehman , Sikandar Azam , Muhammad Asif Hasham , Maida Jameel , Abdulraheem SA Almalki","doi":"10.1016/j.chemphys.2024.112491","DOIUrl":"10.1016/j.chemphys.2024.112491","url":null,"abstract":"<div><div>We studied the electronic and optical properties of pure and Eu-doped CdSe phosphor materials using the first-principles calculation method, which is a feature of Density Functional Theory. The FP-LAPW method was employed for the study as incorporated in the Wien2k code. The GGA + U + SOC method of DFT was used for the first time in our study to investigate the electronic as well as optical characteristics of Eu-doped CdSe materials. Eu doping was done in two different ratios to study the effects of altered dopant concentration. The doping increased the band gap of the pure CdSe parental material. The calculated band gaps in our study were 0.42 eV for pure CdSe, 0.67 eV for a single Eu atom doped in CdSe, and 1.64 eV for two Eu atoms doped in CdSe. The measured electronic and optical characteristics of undoped i.e, pure CdSe and Eu-doped CdSe showed that the doping significantly changed the optical behavior of CdSe, which may be useful for applications in phosphor-converted LEDs.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112491"},"PeriodicalIF":2.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446159","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}
Pub Date : 2024-10-11DOI: 10.1016/j.chemphys.2024.112487
Shuang Zhao , Wei Zeng , Zheng-Tang Liu , Qi-Jun Liu , Dai-He Fan , Juan Gao , Zhen Jiao
A recent study proved that β-ZrNBr displays multifunctionalities in optical applications. Based on DFT, a detailed investigation of crystal structures, electronic, and optical properties were investigated across monolayer, bilayer, trilayer, and bulk forms. Results revealed bulk and 2D ZrNBr are semiconductor nature with indirect band gaps decreasing with layer number. Electronic structure analysis highlighted contributions from Zr-4d, N-2p, and Br-4p hybrids. Optical properties including dielectric function, reflectance, absorption coefficient, and transmittance are also analyzed. The obtained results indicate that 2D and bulk ZrNBr are both p-type transparent conductive materials, with monolayer ZrNBr exhibiting superior performance in transparency and conductivity.
{"title":"Structural, electronic, and optical properties of two-dimensional and bulk ZrNBr from first-principles calculations","authors":"Shuang Zhao , Wei Zeng , Zheng-Tang Liu , Qi-Jun Liu , Dai-He Fan , Juan Gao , Zhen Jiao","doi":"10.1016/j.chemphys.2024.112487","DOIUrl":"10.1016/j.chemphys.2024.112487","url":null,"abstract":"<div><div>A recent study proved that β-ZrNBr displays multifunctionalities in optical applications. Based on DFT, a detailed investigation of crystal structures, electronic, and optical properties were investigated across monolayer, bilayer, trilayer, and bulk forms. Results revealed bulk and 2D ZrNBr are semiconductor nature with indirect band gaps decreasing with layer number. Electronic structure analysis highlighted contributions from Zr-4d, N-2p, and Br-4p hybrids. Optical properties including dielectric function, reflectance, absorption coefficient, and transmittance are also analyzed. The obtained results indicate that 2D and bulk ZrNBr are both p-type transparent conductive materials, with monolayer ZrNBr exhibiting superior performance in transparency and conductivity.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112487"},"PeriodicalIF":2.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442065","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}
The present work theoretically examines the influence of bi-axial strain on functionalized ScYCCl2 monolayer. The indirect to direct band gap transition on tensile conditions and the phase transition from semiconductor to metal on compressive strain have been studied. The analysis of extreme conditions of 10% compressive and 10% tensile strain through phonon and AIMD simulations underscore the kinetic and thermal stability, respectively of the monolayer under strain. These findings assure the possibility of experimental synthesis of the ScYCCl2 monolayer. After metallization, ScYCCl2 MXene is used as an anode of metal-ion (−Na, −K, −Li, −Mg) batteries as it has high theoretical storage capacity and low open circuit voltage. Work function engineering and the strain-dependent optical behavior of the ScYCCl2 monolayer have been examined. The work function of the ScYCCl2 monolayer has been raised under compressive strain and decreased under tensile strain. The Crystal Orbital Hamiltonian Population has been simulated under tensile and compressive strain to check the bond- strengths. Hence, the ScYCCl2 monolayer has the capability to alter its characteristics under strain. The improved optical characteristics recommend its applications in low-dimensional photonic devices and metallization after compressive strain recommends its energy storage applications in metal-ion batteries.
{"title":"Strain Engineering of ScYCCl2 MXene Monolayer and Intercalation of Metal-ions on MXene Surface: A DFT Study","authors":"Nidhi Modi , Yashasvi Naik , S.J. Khengar , H.R. Mahida , D.B. Shah , P.B. Thakor","doi":"10.1016/j.chemphys.2024.112490","DOIUrl":"10.1016/j.chemphys.2024.112490","url":null,"abstract":"<div><div>The present work theoretically examines the influence of bi-axial strain on functionalized ScYCCl<sub>2</sub> monolayer. The indirect to direct band gap transition on tensile conditions and the phase transition from semiconductor to metal on compressive strain have been studied. The analysis of extreme conditions of 10% compressive and 10% tensile strain through phonon and AIMD simulations underscore the kinetic and thermal stability, respectively of the monolayer under strain. These findings assure the possibility of experimental synthesis of the ScYCCl<sub>2</sub> monolayer. After metallization, ScYCCl<sub>2</sub> MXene is used as an anode of metal-ion (−Na, −K, −Li, −Mg) batteries as it has high theoretical storage capacity and low open circuit voltage. Work function engineering and the strain-dependent optical behavior of the ScYCCl<sub>2</sub> monolayer have been examined. The work function of the ScYCCl<sub>2</sub> monolayer has been raised under compressive strain and decreased under tensile strain. The Crystal Orbital Hamiltonian Population has been simulated under tensile and compressive strain to check the bond- strengths. Hence, the ScYCCl<sub>2</sub> monolayer has the capability to alter its characteristics under strain. The improved optical characteristics recommend its applications in low-dimensional photonic devices and metallization after compressive strain recommends its energy storage applications in metal-ion batteries.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112490"},"PeriodicalIF":2.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442068","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}
Light absorption plays important role in different photovoltaics devices. Easy and fast prediction of absorption properties is essential for fast screening of efficient materials. In our pursuit of identifying the optimal model for predicting absorption maxima, we systematically evaluated over 40 machine learning models, employing both molecular descriptors and fingerprints as input features. Notably, models trained on molecular descriptors demonstrated superior predictive capabilities as compared to those relying on molecular fingerprints. This not only showcased the efficacy of molecular descriptors but also highlighted the potential of these models as rapid and efficient alternatives to the density functional theory (DFT) based approaches. The use of machine learning models based on molecular descriptors introduced a level of simplicity and speed in predictions, surpassing the computational demands associated with traditional DFT-based methods. Our introduced framework that is based on machine learning, offers a valuable tool for the easy and fast prediction of properties.
{"title":"Machine learning assisted prediction of absorption maxima in cyclohexene: A comparison using molecular descriptors and fingerprints","authors":"Mudassir Hussain Tahir , Sumaira Naeem , Ashraf Y. Elnaggar , M.H.H. Mahmoud","doi":"10.1016/j.chemphys.2024.112476","DOIUrl":"10.1016/j.chemphys.2024.112476","url":null,"abstract":"<div><div>Light absorption plays important role in different photovoltaics devices. Easy and fast prediction of absorption properties is essential for fast screening of efficient materials. In our pursuit of identifying the optimal model for predicting absorption maxima, we systematically evaluated over 40 machine learning models, employing both molecular descriptors and fingerprints as input features. Notably, models trained on molecular descriptors demonstrated superior predictive capabilities as compared to those relying on molecular fingerprints. This not only showcased the efficacy of molecular descriptors but also highlighted the potential of these models as rapid and efficient alternatives to the density functional theory (DFT) based approaches. The use of machine learning models based on molecular descriptors introduced a level of simplicity and speed in predictions, surpassing the computational demands associated with traditional DFT-based methods. Our introduced framework that is based on machine learning, offers a valuable tool for the easy and fast prediction of properties.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112476"},"PeriodicalIF":2.0,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142427943","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}
Pub Date : 2024-10-02DOI: 10.1016/j.chemphys.2024.112475
P. Mounica , R. Shanmugam , S. Latha , K. Ramya , P. Naga Nandhini , J. Helen Ratna Monica , A. Elangovan , G. Arivazhagan
Fourier Transform Infrared (FTIR) spectra of pure Acetic acid (AcOH), Benzaldehyde (PhCHO) and their binary solutions at various concentration have been recorded. Density functional theory (DFT) calculations using the functional B3LYP/6-311++G (d, p), isosurface, natural bond orbital analysis (NBO) and quantum theory of atoms in molecules (QTAIM) analyses have been performed on dimers of AcOH, PhCHO and their complexes in gas phase. The results of FTIR and DFT calculations have been analysed to identify the dimers present in liquid AcOH/PhCHO and the PhCHO-AcOH complexes present in the binary solutions. The liquid AcOH consists of closed nine dimers with the different interaction schemes. The frequency shift suffered by vibrational bands of AcOH or PhCHO suggest the formation of 1:1 (PhCHO:AcOH) and 1:2 complexes in the binary solutions. The 1:2 complex exist even in 1:3/3:1 binary solution and this indicates that the AcOH dimers remains stable in the diluted solutions.
{"title":"Acetic acid-benzaldehyde solutions: FTIR studies, DFT, isosurface, NBO and QTAIM analyses","authors":"P. Mounica , R. Shanmugam , S. Latha , K. Ramya , P. Naga Nandhini , J. Helen Ratna Monica , A. Elangovan , G. Arivazhagan","doi":"10.1016/j.chemphys.2024.112475","DOIUrl":"10.1016/j.chemphys.2024.112475","url":null,"abstract":"<div><div>Fourier Transform Infrared (FTIR) spectra of pure Acetic acid (AcOH), Benzaldehyde (PhCHO) and their binary solutions at various concentration have been recorded. Density functional theory (DFT) calculations using the functional B3LYP/6-311++G (d, p), isosurface, natural bond orbital analysis (NBO) and quantum theory of atoms in molecules (QTAIM) analyses have been performed on dimers of AcOH, PhCHO and their complexes in gas phase. The results of FTIR and DFT calculations have been analysed to identify the dimers present in liquid AcOH/PhCHO and the PhCHO-AcOH complexes present in the binary solutions. The liquid AcOH consists of closed nine dimers with the different interaction schemes. The frequency shift suffered by vibrational bands of AcOH or PhCHO suggest the formation of 1:1 (PhCHO:AcOH) and 1:2 complexes in the binary solutions. The 1:2 complex exist even in 1:3/3:1 binary solution and this indicates that the AcOH dimers remains stable in the diluted solutions.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112475"},"PeriodicalIF":2.0,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142427945","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}
Pub Date : 2024-10-01DOI: 10.1016/j.chemphys.2024.112472
Deep Solanki , Janvi V. Gajjar , Sarthak J. Trivedi, Debesh R. Roy
A comprehensive investigation on the various properties such as structural, electronic and optical properties of the series of cadmium chalcogenide clusters, viz. CdnXm (n, m = 1–3, X = O, S, Se, Te) using the density functional theory (DFT) is reported in this paper. The electronic properties of all the clusters, including the HOMO-LUMO gap (HLG), ionization potential (IP), electron affinity (EA), chemical hardness (η), and electrophilicity index (ω) has been carried out under conceptual DFT formalism. To explore the extraordinary and/or unusual stable cluster units within the series, the energy gain (ΔE) has been evaluated which reveals Cd3O3 as magically stable cluster among the entire series of CdnXm (n, m = 1–3, X = O, S, Se, Te). Analysis of the frontier molecular orbitals suggests that electron transport is easily facilitated inside the Cd3O3 cluster system. The optical absorption spectra provide evidence that the Cd3O3 cluster is active in the visible range (λ = 472.4 Å) of the electromagnetic spectrum. The origin of the vibrational properties, especially for the visibly active Cd3O3 is addressed through critical study on its infrared spectra, which in turn, will provide experimentalists with valuable insights for its potential synthesis and innovative applications in the domain of optical applications as its assembled materials.
{"title":"Density functional investigation on the Structural, electronic and optical properties of cadmium chalcogenides clusters CdnXm (n = 1–3, m = 1–3; X = O, S, Se, Te)","authors":"Deep Solanki , Janvi V. Gajjar , Sarthak J. Trivedi, Debesh R. Roy","doi":"10.1016/j.chemphys.2024.112472","DOIUrl":"10.1016/j.chemphys.2024.112472","url":null,"abstract":"<div><div>A comprehensive investigation on the various properties such as structural, electronic and optical properties of the series of cadmium chalcogenide clusters, viz. Cd<sub>n</sub>X<sub>m</sub> (n, m = 1–3, X = O, S, Se, Te) using the density functional theory (DFT) is reported in this paper. The electronic properties of all the clusters, including the HOMO-LUMO gap (HLG), ionization potential (IP), electron affinity (EA), chemical hardness (η), and electrophilicity index (ω) has been carried out under conceptual DFT formalism. To explore the extraordinary and/or unusual stable cluster units within the series, the energy gain (<em>ΔE</em>) has been evaluated which reveals Cd<sub>3</sub>O<sub>3</sub> as magically stable cluster among the entire series of Cd<sub>n</sub>X<sub>m</sub> (n, m = 1–3, X = O, S, Se, Te). Analysis of the frontier molecular orbitals suggests that electron transport is easily facilitated inside the Cd<sub>3</sub>O<sub>3</sub> cluster system. The optical absorption spectra provide evidence that the Cd<sub>3</sub>O<sub>3</sub> cluster is active in the visible range (λ = 472.4 Å) of the electromagnetic spectrum. The origin of the vibrational properties, especially for the visibly active Cd<sub>3</sub>O<sub>3</sub> is addressed through critical study on its infrared spectra, which in turn, will provide experimentalists with valuable insights for its potential synthesis and innovative applications in the domain of optical applications as its assembled materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112472"},"PeriodicalIF":2.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142427947","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}
Newly synthesized, cost-effective corrosion inhibitor, N-(4-(1,3-benzothiazol-2-ylcarbamoyl)phenyl)isonicotinamide (BIA) was evaluated for mild steel/1M HCl interface. BIA showed a maximum inhibition efficiency of 90.40 % at 100 ppm and 303 ± 1 K, with efficiency increasing with concentration but decreasing with temperature. Inhibitor’s adsorption followed Langmuir isotherm via physicochemical interactions. Activation parameters revealed BIA retards both metal dissolution and hydrogen evolution held in unimolecular process. Potentiodynamic polarization (PDP) divulged BIA as a mixed-type, impeding charge-transfer. Electrochemical impedance spectra (EIS) confirmed BIA forms a protective double layer, blocking active sites at the interface. Surface analysis supported a protective film formation. Global and local reactivity descriptors using DFT/B3LYP/6-311G++(d,p) were calculated to relate inhibition efficiency with BIA’s electronic properties. Molecular dynamics simulation (MDS) showed an interaction energy of −224.7 kJ/mol between BIA and Fe(1 1 0) at 303 K, with Radial Distribution Function (RDF) showing bond lengths under 3.5 Å, confirming a chemical interaction. Theoretical results align with experimental data.
{"title":"N-(4-(1,3-benzothiazol-2-ylcarbamoyl)phenyl)isonicotinamide as corrosion mitigator for mild steel in 1 M HCl: A multifaceted study integrating synthesis, characterization, and molecular modelling","authors":"Gopal Senthilkumar , Savarinathan Maria Rayappan , Arumugam Ramachandran , Solaiyappan Ayyappan , Pitchai Marimuthu","doi":"10.1016/j.chemphys.2024.112471","DOIUrl":"10.1016/j.chemphys.2024.112471","url":null,"abstract":"<div><div>Newly synthesized, cost-effective corrosion inhibitor, N-(4-(1,3-benzothiazol-2-ylcarbamoyl)phenyl)isonicotinamide (BIA) was evaluated for mild steel/1M HCl interface. BIA showed a maximum inhibition efficiency of 90.40 % at 100 ppm and 303 ± 1 K, with efficiency increasing with concentration but decreasing with temperature. Inhibitor’s adsorption followed Langmuir isotherm via physicochemical interactions. Activation parameters revealed BIA retards both metal dissolution and hydrogen evolution held in unimolecular process. Potentiodynamic polarization (PDP) divulged BIA as a mixed-type, impeding charge-transfer. Electrochemical impedance spectra (EIS) confirmed BIA forms a protective double layer, blocking active sites at the interface. Surface analysis supported a protective film formation. Global and local reactivity descriptors using DFT/B3LYP/6-311G++(d,p) were calculated to relate inhibition efficiency with BIA’s electronic properties. Molecular dynamics simulation (MDS) showed an interaction energy of −224.7 kJ/mol between BIA and Fe(1<!--> <!-->1<!--> <!-->0) at 303 K, with Radial Distribution Function (RDF) showing bond lengths under 3.5 Å, confirming a chemical interaction. Theoretical results align with experimental data.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112471"},"PeriodicalIF":2.0,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142427946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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