Pub Date : 2026-01-30DOI: 10.1021/acs.jpcc.5c07910
Dnyaneshwar D. Ugale, Sidhanath V. Bhosale, Sheshanath V. Bhosale
Pseudocapacitors (PSCs) based on small organic molecule materials have attracted significant research interest due to their structural diversity, tunable redox properties, and ability to support widening the operational potential window, offering higher energy density and rapid power density. Nevertheless, the progress is hindered by their unsatisfactory cycling stability. An approach to tailoring the cycling life of the organic electrode materials for supercapacitors (SCs) is extending π-conjugation of the molecular architecture. To improve the overall performance of the supercapacitor device, the electrode materials, in particular conjugated donor–acceptor–donor (D–A–D)-type molecules, can store both positive and negative charge in a pseudocapacitor device. The D–A–D-type conjugation with good packing could facilitate charge transport and enhance the electrochemical characteristics of the SC cell configurations. In this work, new D–A–D-type 2,7-bis(10-(2-ethylhexyl)-10H-phenothiazin-3-yl) benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (PTZ-NDI-EH) and 2,7-bis(10-(2-hexyldecyl)-10H-phenothiazin-3-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (PTZ-NDI-HD) bearing two different alkyl chains are designed and synthesized. The optimized PTZ-NDI-EH and PTZ-NDI-HD active organic electrode materials in combination with conducting graphite foil (GF) exhibit outstanding functionalities such as higher specific capacitance, higher energy density, and longer cycling stability. Such higher PSC performance could be originating from the molecular packing, higher electronic conductivity, and enhanced charge delocalization during the Faradaic reversible redox processes. The higher cycling stability could be attributed to efficient ion transportation. In addition, the alkyl chain length influences the electrochemical properties of PTZ-NDI-EH and PTZ-NDI-HD. The increase in contact angle of PTZ-NDI-HD (higher alkyl chain length) leads to the reduction of the specific capacitance compared to PTZ-NDI-EH (lower alkyl chain length). This provides the basis for the wettability of the electrode in the presence of aqueous electrolytes and their impact on the electrochemical properties. These results indicate that the D–A–D materials design and their applications contribute to the development of high-performance electrical energy storage (EES) devices.
基于小有机分子材料的假电容器（PSCs）由于其结构多样性、可调节的氧化还原特性以及支持扩大工作电位窗口的能力，提供更高的能量密度和快速的功率密度，引起了人们的极大研究兴趣。然而，由于其不理想的循环稳定性，这一进展受到阻碍。扩大分子结构的π共轭是提高超级电容器有机电极材料循环寿命的一种途径。为了提高超级电容器器件的整体性能，电极材料，特别是共轭供体-受体-供体（D-A-D）型分子，可以在假电容器器件中同时存储正电荷和负电荷。具有良好填料的d - a - d型共轭可以促进电荷传输，提高SC电池结构的电化学特性。本文设计并合成了新型d - a - d型2,7-二（10-（2-乙基己基）- 10h -吩噻嗪-3-基）苯并[lmn][3,8]菲罗啉-1,3,6,8(2H,7H)-四酮（PTZ-NDI-EH）和2,7-二（10-（2-己基癸基）- 10h -吩噻嗪-3-基）苯并[lmn][3,8]菲罗啉-1,3,6,8(2H,7H)-四酮（PTZ-NDI-HD）。优化后的PTZ-NDI-EH和PTZ-NDI-HD活性有机电极材料与导电石墨箔（GF）结合，表现出更高的比电容、更高的能量密度和更长的循环稳定性。这种更高的PSC性能可能源于分子包装、更高的电子导电性以及法拉第可逆氧化还原过程中电荷离域的增强。较高的循环稳定性可归因于高效的离子运输。此外，烷基链长度对PTZ-NDI-EH和PTZ-NDI-HD的电化学性能也有影响。较高烷基链长度的PTZ-NDI-HD与较低烷基链长度的PTZ-NDI-EH相比，接触角增大导致比电容减小。这为电极在水电解质存在下的润湿性及其对电化学性能的影响提供了基础。这些结果表明，D-A-D材料的设计及其应用有助于高性能电能存储（EES）器件的发展。
{"title":"Unveiling the Effect of Varying Chain Length and Wettability on the Charge-Storage Performance in Donor–Acceptor–Donor-Type Electrode-Based Pseudocapacitors","authors":"Dnyaneshwar D. Ugale, Sidhanath V. Bhosale, Sheshanath V. Bhosale","doi":"10.1021/acs.jpcc.5c07910","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07910","url":null,"abstract":"Pseudocapacitors (PSCs) based on small organic molecule materials have attracted significant research interest due to their structural diversity, tunable redox properties, and ability to support widening the operational potential window, offering higher energy density and rapid power density. Nevertheless, the progress is hindered by their unsatisfactory cycling stability. An approach to tailoring the cycling life of the organic electrode materials for supercapacitors (SCs) is extending π-conjugation of the molecular architecture. To improve the overall performance of the supercapacitor device, the electrode materials, in particular conjugated donor–acceptor–donor (D–A–D)-type molecules, can store both positive and negative charge in a pseudocapacitor device. The D–A–D-type conjugation with good packing could facilitate charge transport and enhance the electrochemical characteristics of the SC cell configurations. In this work, new D–A–D-type 2,7-bis(10-(2-ethylhexyl)-10<i>H</i>-phenothiazin-3-yl) benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (PTZ-NDI-EH) and 2,7-bis(10-(2-hexyldecyl)-10H-phenothiazin-3-yl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2<i>H</i>,7<i>H</i>)-tetraone (PTZ-NDI-HD) bearing two different alkyl chains are designed and synthesized. The optimized PTZ-NDI-EH and PTZ-NDI-HD active organic electrode materials in combination with conducting graphite foil (GF) exhibit outstanding functionalities such as higher specific capacitance, higher energy density, and longer cycling stability. Such higher PSC performance could be originating from the molecular packing, higher electronic conductivity, and enhanced charge delocalization during the Faradaic reversible redox processes. The higher cycling stability could be attributed to efficient ion transportation. In addition, the alkyl chain length influences the electrochemical properties of PTZ-NDI-EH and PTZ-NDI-HD. The increase in contact angle of PTZ-NDI-HD (higher alkyl chain length) leads to the reduction of the specific capacitance compared to PTZ-NDI-EH (lower alkyl chain length). This provides the basis for the wettability of the electrode in the presence of aqueous electrolytes and their impact on the electrochemical properties. These results indicate that the D–A–D materials design and their applications contribute to the development of high-performance electrical energy storage (EES) devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089638","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 : 2026-01-30DOI: 10.1021/acs.jpcc.5c08632
Maohua Quan, Yuting Qiu, Zhou Yang
In Raman spectroscopy, the optimal signal is obtained when the sample is irradiated by a laser at normal incidence. Ensuring both signal stability and high sensitivity for capturing analyte molecules on nonflat or tilted substrates remains difficult, especially in the process of rapid testing. Here, 3D hemispherical polydimethylsiloxane (PDMS) substrate with bioinspired compound-eye structure was fabricated by utilizing the liquid–liquid interface self-assembly and transfer technique. Using Au monolayer films decorated PDMS substrate as a surface-enhanced Raman scattering (SERS) substrate. The rotational symmetry of the bioinspired SERS substrate architecture enables stable SERS performance even under substrate tilting from 0 to 75°, demonstrating excellent suitability for field-based detection applications. The hemispherical SERS substrate demonstrated a minimum detectable urea concentration of 10–5 M, which is significantly lower than the minimum urea level (10–3 M) in the tear fluid of the body.
{"title":"Stable Light-Trapping SERS Substrates with Bioinspired Arrays for Biochemical Sensing","authors":"Maohua Quan, Yuting Qiu, Zhou Yang","doi":"10.1021/acs.jpcc.5c08632","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08632","url":null,"abstract":"In Raman spectroscopy, the optimal signal is obtained when the sample is irradiated by a laser at normal incidence. Ensuring both signal stability and high sensitivity for capturing analyte molecules on nonflat or tilted substrates remains difficult, especially in the process of rapid testing. Here, 3D hemispherical polydimethylsiloxane (PDMS) substrate with bioinspired compound-eye structure was fabricated by utilizing the liquid–liquid interface self-assembly and transfer technique. Using Au monolayer films decorated PDMS substrate as a surface-enhanced Raman scattering (SERS) substrate. The rotational symmetry of the bioinspired SERS substrate architecture enables stable SERS performance even under substrate tilting from 0 to 75°, demonstrating excellent suitability for field-based detection applications. The hemispherical SERS substrate demonstrated a minimum detectable urea concentration of 10<sup>–5</sup> M, which is significantly lower than the minimum urea level (10<sup>–3</sup> M) in the tear fluid of the body.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"284 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089589","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 : 2026-01-29DOI: 10.1021/acs.jpcc.5c07253
J. Hingies Monisha, Vasumathi Velachi, Prabal K. Maiti
Ensuring the stability of the AuNP-gene complex until it reaches the target sites is a crucial factor for the success of gene therapy. Although different AuNP sizes and AuNP-to-DNA ratios are investigated for specific therapeutic needs, their role in the stability and packaging of AuNP-DNA complex remains unclear. In this study, we employ all-atom molecular dynamics simulations to investigate the influence of cationic ligand-functionalized AuNP (CAuNP) size and CAuNP-to-DNA ratio on DNA wrapping and binding affinity. The obtained results show that a single DNA interacting with smaller CAuNPs exhibits greater bending and wrapping due to their higher curvature. However, when two DNAs bind to smaller CAuNPs, electrostatic repulsion prevents the effective wrapping, which leads the DNAs to twist from their original orientation. Such behavior is not observed with larger CAuNPs since their increased size may mitigate repulsive forces. Further, the analysis on axial bending angle reveals that smaller AuNPs induce sharper DNA bending and larger AuNPs promote smoother bending. In addition, the potential of mean force (PMF) analysis confirms a stronger DNA binding affinity for larger AuNPs, with affinity decreasing when two DNAs attach to a single CAuNP. Our results from the DNA loading capacity calculations provide insights into the maximum number of DNA molecules that can be loaded onto CAuNPs of a given size. These findings offer key insights into optimizing the size of AuNP and DNA-to-AuNP ratios for the development of efficient gene delivery systems.
{"title":"Effect of Gold Nanoparticle Size and DNA Concentration on DNA-Nanoparticles Complexation: A Molecular Dynamics Study","authors":"J. Hingies Monisha, Vasumathi Velachi, Prabal K. Maiti","doi":"10.1021/acs.jpcc.5c07253","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07253","url":null,"abstract":"Ensuring the stability of the AuNP-gene complex until it reaches the target sites is a crucial factor for the success of gene therapy. Although different AuNP sizes and AuNP-to-DNA ratios are investigated for specific therapeutic needs, their role in the stability and packaging of AuNP-DNA complex remains unclear. In this study, we employ all-atom molecular dynamics simulations to investigate the influence of cationic ligand-functionalized AuNP (CAuNP) size and CAuNP-to-DNA ratio on DNA wrapping and binding affinity. The obtained results show that a single DNA interacting with smaller CAuNPs exhibits greater bending and wrapping due to their higher curvature. However, when two DNAs bind to smaller CAuNPs, electrostatic repulsion prevents the effective wrapping, which leads the DNAs to twist from their original orientation. Such behavior is not observed with larger CAuNPs since their increased size may mitigate repulsive forces. Further, the analysis on axial bending angle reveals that smaller AuNPs induce sharper DNA bending and larger AuNPs promote smoother bending. In addition, the potential of mean force (PMF) analysis confirms a stronger DNA binding affinity for larger AuNPs, with affinity decreasing when two DNAs attach to a single CAuNP. Our results from the DNA loading capacity calculations provide insights into the maximum number of DNA molecules that can be loaded onto CAuNPs of a given size. These findings offer key insights into optimizing the size of AuNP and DNA-to-AuNP ratios for the development of efficient gene delivery systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"85 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070602","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c04627
Jing Xu, Wanlin Guo, Yufeng Guo
Developing catalysts based on graphene heterostructures is an attractive aspect for advancing the application of graphene. Our extensive first-principles calculations and ab initio molecular dynamics simulations reveal that the catalytic capability of graphene/Cu heterostructures for the electrochemical oxygen evolution reaction (OER) can be activated and significantly enhanced by the synergistic effect of introducing Stone–Wales (SW) defects into graphene and applying biaxial compressive strains to the heterostructures. The overpotential of the SW-defected graphene/Cu heterostructure for the OER decreases to 0.39 V under a biaxial compressive strain of −3%, which is lower than most theoretical overpotentials obtained when using graphene heterostructures as catalysts. The alteration and improvement in the catalytic capability of SW-defected graphene/Cu heterostructures under compressive strains are mainly attributed to the facilitated desorption of intermediates on graphene, the decreased reaction activation energy, and the charge transfer from the SW defect sites to the Cu substrates.
{"title":"Catalytic Capability of Graphene/Cu Heterostructures for Oxygen Evolution Reaction Activated by the Synergistic Effect of Defects and Strain","authors":"Jing Xu, Wanlin Guo, Yufeng Guo","doi":"10.1021/acs.jpcc.5c04627","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04627","url":null,"abstract":"Developing catalysts based on graphene heterostructures is an attractive aspect for advancing the application of graphene. Our extensive first-principles calculations and <i>ab initio</i> molecular dynamics simulations reveal that the catalytic capability of graphene/Cu heterostructures for the electrochemical oxygen evolution reaction (OER) can be activated and significantly enhanced by the synergistic effect of introducing Stone–Wales (SW) defects into graphene and applying biaxial compressive strains to the heterostructures. The overpotential of the SW-defected graphene/Cu heterostructure for the OER decreases to 0.39 V under a biaxial compressive strain of −3%, which is lower than most theoretical overpotentials obtained when using graphene heterostructures as catalysts. The alteration and improvement in the catalytic capability of SW-defected graphene/Cu heterostructures under compressive strains are mainly attributed to the facilitated desorption of intermediates on graphene, the decreased reaction activation energy, and the charge transfer from the SW defect sites to the Cu substrates.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089590","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c08205
Shu-Hui Guan, Yi-Wen Wei, Cheng Shang, Zhi-Pan Liu
Scandia (Sc) and yttria (Y) codoped zirconia (ScYSZ) emerged as a promising candidate for high-performance solid electrolyte materials utilized in intermediate-temperature solid oxide fuel cells (IT-SOFCs). While it exhibits a record-high ionic conductivity (∼0.10 S/cm at 800 °C), the physical origin of the superior performance remains poorly understood, limiting the further optimization and the application in IT-SOFC. Here, we construct the Sc–Y–Zr–O global neural network potential and explore systematically the thermodynamic landscape of ScYSZ across 65 different compositions (6.7–14.3 mol % dopants). From millions of candidate structures, we identify a thermodynamically stable cubic phase region at Sc/Y < 1 with Y2O3 ≥ 8 mol %. Large-scale molecular dynamics simulations further show that ScYSZ at Sc2O3 = 3 mol % and Y2O3 = 8 mol % yields an exceptional ionic conductivity of 0.13 S/cm at 800 °C, surpassing conventional 8 mol % Y-stabilized zirconia (YSZ) by an order of magnitude. Our analysis reveals that the presence of Sc not only increases the Ov concentration by allowing ⟨111⟩ Ov–Ov pairs but also reduces the oxygen migration barriers markedly. Our results not only pinpoint the optimal ScYSZ composition for IT-SOFC applications theoretically but also establish a general framework for the rational design of advanced solid electrolyte materials.
{"title":"Scandia as the Oxygen Vacancy Stabilizer to Boost the Ionic Conductivity of Sc–Y-Codoped Zirconia","authors":"Shu-Hui Guan, Yi-Wen Wei, Cheng Shang, Zhi-Pan Liu","doi":"10.1021/acs.jpcc.5c08205","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08205","url":null,"abstract":"Scandia (Sc) and yttria (Y) codoped zirconia (ScYSZ) emerged as a promising candidate for high-performance solid electrolyte materials utilized in intermediate-temperature solid oxide fuel cells (IT-SOFCs). While it exhibits a record-high ionic conductivity (∼0.10 S/cm at 800 °C), the physical origin of the superior performance remains poorly understood, limiting the further optimization and the application in IT-SOFC. Here, we construct the Sc–Y–Zr–O global neural network potential and explore systematically the thermodynamic landscape of ScYSZ across 65 different compositions (6.7–14.3 mol % dopants). From millions of candidate structures, we identify a thermodynamically stable cubic phase region at Sc/Y < 1 with Y<sub>2</sub>O<sub>3</sub> ≥ 8 mol %. Large-scale molecular dynamics simulations further show that ScYSZ at Sc<sub>2</sub>O<sub>3</sub> = 3 mol % and Y<sub>2</sub>O<sub>3</sub> = 8 mol % yields an exceptional ionic conductivity of 0.13 S/cm at 800 °C, surpassing conventional 8 mol % Y-stabilized zirconia (YSZ) by an order of magnitude. Our analysis reveals that the presence of Sc not only increases the O<sub>v</sub> concentration by allowing ⟨111⟩ O<sub>v</sub>–O<sub>v</sub> pairs but also reduces the oxygen migration barriers markedly. Our results not only pinpoint the optimal ScYSZ composition for IT-SOFC applications theoretically but also establish a general framework for the rational design of advanced solid electrolyte materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"56 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089591","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c08343
Yitao He, Jiří Červenka
Electrochemistry lies at the heart of modern energy technologies, yet connecting atomic-level insights to macroscopic performance remains an enduring challenge. Quantum-based simulations, such as density functional theory, have illuminated many fundamental processes, but their reach is limited by the complexity of real electrochemical environments. Bridging these scales requires a new conceptual framework that can expose the hidden connections between theory and experiment. Here, we argue that the thoughtful integration of artificial intelligence (AI) can transform electrochemical research by unifying theory, experiment, and data-driven inference. AI-assisted frameworks can accelerate convergence between computation and experiment, revealing hidden physical relationships and enabling closed-loop discovery. Realizing this vision will require developing transparent, interpretable AI models that earn the same scientific trust as human reasoning, unlocking deeper understanding and innovation across the electrochemical sciences.
{"title":"How Artificial Intelligence Can Advance Electrochemical Science and Identify Water Molecule Orientation on Platinum Electrodes","authors":"Yitao He, Jiří Červenka","doi":"10.1021/acs.jpcc.5c08343","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08343","url":null,"abstract":"Electrochemistry lies at the heart of modern energy technologies, yet connecting atomic-level insights to macroscopic performance remains an enduring challenge. Quantum-based simulations, such as density functional theory, have illuminated many fundamental processes, but their reach is limited by the complexity of real electrochemical environments. Bridging these scales requires a new conceptual framework that can expose the hidden connections between theory and experiment. Here, we argue that the thoughtful integration of artificial intelligence (AI) can transform electrochemical research by unifying theory, experiment, and data-driven inference. AI-assisted frameworks can accelerate convergence between computation and experiment, revealing hidden physical relationships and enabling closed-loop discovery. Realizing this vision will require developing transparent, interpretable AI models that earn the same scientific trust as human reasoning, unlocking deeper understanding and innovation across the electrochemical sciences.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056993","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c08141
Rens Cuijpers, Wietse F. M. van Geel, Dorothée S. Mader, K. Danique Grevink, Matthijs van Velzen, Martin Lutz, Stefan C. J. Meskers
Materials consisting of organic dye molecules play an important role as pigments, as active layer in organic light emitting diodes or solar cells, and as bistable medium in optical transistors and switches. Yet there is currently no working protocol to accurately predict one of the most basic optical properties of these solids: their reflection spectrum. Here we develop a method to calculate the reflection spectrum of crystals of dye molecules based on the crystal structure and optical absorption of the dye in solution. We treat the interaction between light and matter in the crystals as strong. Electromagnetic four-potentials are gauged consistently, and their boundary conditions at the reflecting interface are derived. Finally, we include both excitonic and charge transfer interactions between molecules in the crystals. We test our approach on a large data set of reflection spectra and crystal structures including several industrial pigments.
{"title":"Optical Reflection of Crystals of Dye Molecules and Strong Coupling between Light and Matter","authors":"Rens Cuijpers, Wietse F. M. van Geel, Dorothée S. Mader, K. Danique Grevink, Matthijs van Velzen, Martin Lutz, Stefan C. J. Meskers","doi":"10.1021/acs.jpcc.5c08141","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08141","url":null,"abstract":"Materials consisting of organic dye molecules play an important role as pigments, as active layer in organic light emitting diodes or solar cells, and as bistable medium in optical transistors and switches. Yet there is currently no working protocol to accurately predict one of the most basic optical properties of these solids: their reflection spectrum. Here we develop a method to calculate the reflection spectrum of crystals of dye molecules based on the crystal structure and optical absorption of the dye in solution. We treat the interaction between light and matter in the crystals as strong. Electromagnetic four-potentials are gauged consistently, and their boundary conditions at the reflecting interface are derived. Finally, we include both excitonic and charge transfer interactions between molecules in the crystals. We test our approach on a large data set of reflection spectra and crystal structures including several industrial pigments.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"55 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056959","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c06506
Rashid Rafeek V Valappil, Sayan Maity, Ashwini Anshu, Lavanya M. Ramaniah, Varadharajan Srinivasan
Varying the rate at which pressure is applied to a crystal is known to yield different pressure-induced polymorphic structures in experiments. In this work, we investigate the effect of pressure increase rate on pressure-induced polymerization in crystalline acrylamide, using room temperature constant pressure ab initio molecular dynamics simulations. Simulations performed with two different compression rates revealed very different structural evolutions of the system at lower pressures. Fast (nonequilibrated) pressure increase yields disordered (polymer) structures with unanticipated linkages for pressures up to 67 GPa. On the other hand, slow (quasi-static) pressure increase gives no new structures until 64 GPa. At pressures greater than 67 GPa, both pathways converge toward an ordered 3-dimensional polymer through a hierarchical mechanism involving 1-dimensional polymeric intermediates. The structural and electronic details of the mechanisms leading to polymerization are discussed.
{"title":"Compression Rate Dependence and Hierarchical Mechanism in the Pressure-Induced Polymerization of Acrylamide: Insights from Ab Initio Molecular Dynamics","authors":"Rashid Rafeek V Valappil, Sayan Maity, Ashwini Anshu, Lavanya M. Ramaniah, Varadharajan Srinivasan","doi":"10.1021/acs.jpcc.5c06506","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06506","url":null,"abstract":"Varying the rate at which pressure is applied to a crystal is known to yield different pressure-induced polymorphic structures in experiments. In this work, we investigate the effect of pressure increase rate on pressure-induced polymerization in crystalline acrylamide, using room temperature constant pressure <i>ab initio</i> molecular dynamics simulations. Simulations performed with two different compression rates revealed very different structural evolutions of the system at lower pressures. Fast (nonequilibrated) pressure increase yields disordered (polymer) structures with unanticipated linkages for pressures up to 67 GPa. On the other hand, slow (quasi-static) pressure increase gives no new structures until 64 GPa. At pressures greater than 67 GPa, both pathways converge toward an ordered 3-dimensional polymer through a hierarchical mechanism involving 1-dimensional polymeric intermediates. The structural and electronic details of the mechanisms leading to polymerization are discussed.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070603","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c07043
Andreas Ziegler, Chiara I. Wagner, Hao Chen, Matthias A. Blatnik, Alexander Wolfram, Anne Brandmeier, Zdeněk Jakub, Michele Riva, Jiri Pavelec, Michael Schmid, Ulrike Diebold, Bernd Meyer, Margareta Wagner
Research on sustainable energy has intensified to reduce greenhouse gas emissions, especially CO2. One promising strategy is the catalytic reduction of CO2 to methanol, and indium oxide (In2O3) has emerged as a highly efficient catalyst, with high turnover rates and selectivity. This work investigates methanol, the end product of CO2 reduction, and its interaction with the In2O3(111) surface. Utilizing an ultrahigh vacuum (UHV) environment, this study combines temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), noncontact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The coverages investigated range from 1 to 12 methanol molecules per unit cell. The results are compared to water adsorption on In2O3(111), as the chemical behavior of both molecules is similar in many respects. At low coverage, the adsorption patterns and interactions with the In2O3(111) surface mirror those seen with water, including dissociative and molecular adsorption. The first three methanol molecules dissociate at specific sites within the surface unit cell, while molecular adsorption becomes favored for subsequent molecules at temperatures below 300 K. At the highest coverage (before multilayer adsorption) methanol and water exhibit distinct structures due to their differing hydrogen bonding capabilities.
{"title":"Revealing the Intricate Structure of Surface Phases of Methanol on In2O3(111)","authors":"Andreas Ziegler, Chiara I. Wagner, Hao Chen, Matthias A. Blatnik, Alexander Wolfram, Anne Brandmeier, Zdeněk Jakub, Michele Riva, Jiri Pavelec, Michael Schmid, Ulrike Diebold, Bernd Meyer, Margareta Wagner","doi":"10.1021/acs.jpcc.5c07043","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07043","url":null,"abstract":"Research on sustainable energy has intensified to reduce greenhouse gas emissions, especially CO<sub>2</sub>. One promising strategy is the catalytic reduction of CO<sub>2</sub> to methanol, and indium oxide (In<sub>2</sub>O<sub>3</sub>) has emerged as a highly efficient catalyst, with high turnover rates and selectivity. This work investigates methanol, the end product of CO<sub>2</sub> reduction, and its interaction with the In<sub>2</sub>O<sub>3</sub>(111) surface. Utilizing an ultrahigh vacuum (UHV) environment, this study combines temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), noncontact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The coverages investigated range from 1 to 12 methanol molecules per unit cell. The results are compared to water adsorption on In<sub>2</sub>O<sub>3</sub>(111), as the chemical behavior of both molecules is similar in many respects. At low coverage, the adsorption patterns and interactions with the In<sub>2</sub>O<sub>3</sub>(111) surface mirror those seen with water, including dissociative and molecular adsorption. The first three methanol molecules dissociate at specific sites within the surface unit cell, while molecular adsorption becomes favored for subsequent molecules at temperatures below 300 K. At the highest coverage (before multilayer adsorption) methanol and water exhibit distinct structures due to their differing hydrogen bonding capabilities.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"80 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089770","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 : 2026-01-28DOI: 10.1021/acs.jpcc.5c07216
Lu Yang, Huabing Shu, Jian Zhang, Jianping Li, Gang Zhang, Kai Ren
Low interfacial thermal conductance often emerges as a primary barrier to effective heat management in advanced nanodevices. This study examines how topological defects affect the interfacial thermal conductance of graphene/SiC lateral heterostructure, utilizing nonequilibrium molecular dynamics simulations. The significant lattice mismatch between graphene and SiC results in a pristine interface that experiences severe strain and structural distortion, ultimately reducing the level of phonon transmission. By introduction of 5|8|5 topological defects, the interfacial deformation is effectively alleviated, thereby improving phonon coupling across the boundary. The results reveal an unconventional increase in interfacial thermal conductance, with the maximal value achieved when three defects are incorporated, representing a 61% improvement compared with the pristine interface. However, an excessive number of defects can lead to a reduction in the thermal conductivity. These findings demonstrate that controlled defect engineering offers a tunable pathway to optimize interfacial heat transport in 2D heterostructures, providing valuable insights for thermal management in nanoscale devices.
{"title":"Manipulation of Abnormal Thermal Conductance at the Graphene/SiC Interface through Topological Defects","authors":"Lu Yang, Huabing Shu, Jian Zhang, Jianping Li, Gang Zhang, Kai Ren","doi":"10.1021/acs.jpcc.5c07216","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07216","url":null,"abstract":"Low interfacial thermal conductance often emerges as a primary barrier to effective heat management in advanced nanodevices. This study examines how topological defects affect the interfacial thermal conductance of graphene/SiC lateral heterostructure, utilizing nonequilibrium molecular dynamics simulations. The significant lattice mismatch between graphene and SiC results in a pristine interface that experiences severe strain and structural distortion, ultimately reducing the level of phonon transmission. By introduction of 5|8|5 topological defects, the interfacial deformation is effectively alleviated, thereby improving phonon coupling across the boundary. The results reveal an unconventional increase in interfacial thermal conductance, with the maximal value achieved when three defects are incorporated, representing a 61% improvement compared with the pristine interface. However, an excessive number of defects can lead to a reduction in the thermal conductivity. These findings demonstrate that controlled defect engineering offers a tunable pathway to optimize interfacial heat transport in 2D heterostructures, providing valuable insights for thermal management in nanoscale devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"40 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056958","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：