Aoife Lucid, Javier F. Troncoso, Jorge Kohanoff, Stephen Fahy, Ivana Savic
The nanostructuring of thermoelectric materials is a well-established method of suppressing lattice thermal conductivity. However, our understanding of the interfaces that form as a result of nanostructure engineering is still limited. In this work, we utilise a simple two-body pair potential to calculate the thermal boundary resistance of basal plane twin boundaries in ce{Bi2Te3} at 300 K using reverse non-equilibrium molecular dynamics simulations. The considered interatomic potential gives an excellent description of the twin boundary formation energies and the lattice thermal conductivity of bulk ce{Bi2Te3}. Using this potential, we find that the twin boundary located at the Bi layer is not thermally stable (unlike those located at the Te layers), and undergoes a phase transition into two distinct structures. We compare the thermal boundary resistance across these different twin boundaries and link the observed trends to overall geometry, van der Waals gap sizes and degree of structural disorder in atomic layers near the boundary.
{"title":"Structure and thermal boundary resistance of basal plane twin boundaries in Bi2Te3","authors":"Aoife Lucid, Javier F. Troncoso, Jorge Kohanoff, Stephen Fahy, Ivana Savic","doi":"10.1039/d4cp04211e","DOIUrl":"https://doi.org/10.1039/d4cp04211e","url":null,"abstract":"The nanostructuring of thermoelectric materials is a well-established method of suppressing lattice thermal conductivity. However, our understanding of the interfaces that form as a result of nanostructure engineering is still limited. In this work, we utilise a simple two-body pair potential to calculate the thermal boundary resistance of basal plane twin boundaries in ce{Bi2Te3} at 300 K using reverse non-equilibrium molecular dynamics simulations. The considered interatomic potential gives an excellent description of the twin boundary formation energies and the lattice thermal conductivity of bulk ce{Bi2Te3}. Using this potential, we find that the twin boundary located at the Bi layer is not thermally stable (unlike those located at the Te layers), and undergoes a phase transition into two distinct structures. We compare the thermal boundary resistance across these different twin boundaries and link the observed trends to overall geometry, van der Waals gap sizes and degree of structural disorder in atomic layers near the boundary.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"90 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819145","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}
Yolimar Gil, María José Maldonado, Ricardo Costa de Santana, Andres Vega, Pablo Fuentealba, Daniel Aravena
A protocol to correct ab initio calculated luminescence spectra of NdIII complexes is proposed. The emission spectrum of [NdIII(bipy)(tta)3] was measured to calibrate the optimal correction for the Racah parameters on top of a CASSCF calculation to attain the best energetic placement of the 4F3/2 → 4I13/2-9/2 emission lines. As interelectronic repulsion is the most important source of error in this calcuations, this straightforward correction results in an accurate placement of transitions, allowing to assign a complex spectral shape in terms of its underlying transitions. Finally, the correction derived for [NdIII(bipy)(tta)3] was directly applied to a different NdIII complex, demostrating the broad use of this approach
{"title":"Improvement of electronic structure calculations for the interpretation of emission spectrum of NdIII complexes","authors":"Yolimar Gil, María José Maldonado, Ricardo Costa de Santana, Andres Vega, Pablo Fuentealba, Daniel Aravena","doi":"10.1039/d5cp00508f","DOIUrl":"https://doi.org/10.1039/d5cp00508f","url":null,"abstract":"A protocol to correct ab initio calculated luminescence spectra of NdIII complexes is proposed. The emission spectrum of [NdIII(bipy)(tta)3] was measured to calibrate the optimal correction for the Racah parameters on top of a CASSCF calculation to attain the best energetic placement of the 4F3/2 → 4I13/2-9/2 emission lines. As interelectronic repulsion is the most important source of error in this calcuations, this straightforward correction results in an accurate placement of transitions, allowing to assign a complex spectral shape in terms of its underlying transitions. Finally, the correction derived for [NdIII(bipy)(tta)3] was directly applied to a different NdIII complex, demostrating the broad use of this approach","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813642","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}
Particle-bubble flows are commonly found in industrial processes such as mineral flotation, catalytic reactors, and fluidized beds. This study reports the behavior of particles impacting adhered bubbles on surfaces and resulting in their detachment. The effect of particle diameter, particle collision velocity, and bubble height on bubble dynamics was investigated. To connect the three factors together, the Weber number of the particles was fitted with the different heights of bubbles to derive a critical detachment curve for bubbles at varying particle diameters. The results indicate that the detachment height of bubbles is inversely proportional to the collision velocity and diameter of the particles. Additionally, among these three factors, the primary force influencing the bubble detachment time is the capillary force of the particles.
{"title":"Experimental study of particle collision on bubble dynamics behavior","authors":"Xiaoxiang Li, Ying Zhang, Weichen Tang, Xin Chen, Fei Dong","doi":"10.1039/d5cp00938c","DOIUrl":"https://doi.org/10.1039/d5cp00938c","url":null,"abstract":"Particle-bubble flows are commonly found in industrial processes such as mineral flotation, catalytic reactors, and fluidized beds. This study reports the behavior of particles impacting adhered bubbles on surfaces and resulting in their detachment. The effect of particle diameter, particle collision velocity, and bubble height on bubble dynamics was investigated. To connect the three factors together, the Weber number of the particles was fitted with the different heights of bubbles to derive a critical detachment curve for bubbles at varying particle diameters. The results indicate that the detachment height of bubbles is inversely proportional to the collision velocity and diameter of the particles. Additionally, among these three factors, the primary force influencing the bubble detachment time is the capillary force of the particles.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813745","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}
Hao Zuo, Yuqin Zhang, Guijun Du, Chuxi Ding, Guoying Feng
In this study, we employed HSE06 hybrid density functional theory with high precision to investigate ZnSe single-walled and double-walled nanotubes of different chiral sizes. We calculated the structural stability, electronic properties, band edge positions, carrier mobility and optical properties of single-walled nanotubes (SWZSNTs) with (n, n) armchair and (n, 0) zigzag configurations, as well as (n, 0) @ (m, 0) double-walled nanotubes (DWZSNTs). It was found that as the diameter increases, the energy band of SWZSNTs decreases, and both the conduction and valence bands move downward simultaneously. Due to the lower formation energy and strain energy of the zigzag structure, we chose to establish DWZSNTs based on it. We found that while fixing the outer wall, the wall spacing is proportional to the energy band. In addition, DWZSNTs with suitable chirality have a narrower band gap and a band edge that is more closely aligned with the water splitting oxidation-reduction potential compared to SWZSNTs. At the same time, they have a type II heterojunction energy band structure. Through the theory of deformation potential, it was concluded that DWZSNTs exhibit excellent carrier mobility almost identical to that of two-dimensional structures. Finally, we calculated that DWZSNTs have superior optical absorption performance than SWZSNTs. Therefore, DWZSNTs are more suitable as photocatalysts for water splitting.
{"title":"First principles study of structural and electronic properties of single and double-walled ZnSe nanotubes, toward the photocatalyst application","authors":"Hao Zuo, Yuqin Zhang, Guijun Du, Chuxi Ding, Guoying Feng","doi":"10.1039/d5cp00704f","DOIUrl":"https://doi.org/10.1039/d5cp00704f","url":null,"abstract":"In this study, we employed HSE06 hybrid density functional theory with high precision to investigate ZnSe single-walled and double-walled nanotubes of different chiral sizes. We calculated the structural stability, electronic properties, band edge positions, carrier mobility and optical properties of single-walled nanotubes (SWZSNTs) with (n, n) armchair and (n, 0) zigzag configurations, as well as (n, 0) @ (m, 0) double-walled nanotubes (DWZSNTs). It was found that as the diameter increases, the energy band of SWZSNTs decreases, and both the conduction and valence bands move downward simultaneously. Due to the lower formation energy and strain energy of the zigzag structure, we chose to establish DWZSNTs based on it. We found that while fixing the outer wall, the wall spacing is proportional to the energy band. In addition, DWZSNTs with suitable chirality have a narrower band gap and a band edge that is more closely aligned with the water splitting oxidation-reduction potential compared to SWZSNTs. At the same time, they have a type II heterojunction energy band structure. Through the theory of deformation potential, it was concluded that DWZSNTs exhibit excellent carrier mobility almost identical to that of two-dimensional structures. Finally, we calculated that DWZSNTs have superior optical absorption performance than SWZSNTs. Therefore, DWZSNTs are more suitable as photocatalysts for water splitting.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813743","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}
Bharat Poudel, Joshua Whiting, Juan M. Vanegas, Susan B. Rempe
Fentanyl is a synthetic opioid with higher potency compared to morphine and heroin, making it an essential drug for pain management and also an abused drug. Beyond fentanyl, derivatives, such as o-fluoro fentanyl and furanyl fentanyl, also possess similar potency and present a significant risk of misuse, but without medical utility. A major challenge for law enforcement is detecting fentanyl and its analogues in their degraded forms. While the degradation fragments of fentanyl are well- known, those of its analogues are not as well studied. Here, we investigated the thermal degradation pathways of fentanyl analogues using extensive ab initio molecular dynamics simulations combined with enhanced sampling techniques, including multiple walker metadynamics. We calculated the free energy profiles for each bond previously identified as a potential degradation site to map out the thermodynamic driving forces. Additionally, we estimated the forward attempt rate of each bond degradation reaction to gain insights into the kinetics of those degradation processes. Our results showed that, despite high similarity in structure, the bond breaking pathways differ for the analogues compared with fentanyl. We also observe that traditional force fields with fixed charges are insufficient for studies of fentanyl and its analogues due to polarizability of the electronic structure.
{"title":"Thermal Degradation Energetics of Fentanyl Analogues","authors":"Bharat Poudel, Joshua Whiting, Juan M. Vanegas, Susan B. Rempe","doi":"10.1039/d5cp00024f","DOIUrl":"https://doi.org/10.1039/d5cp00024f","url":null,"abstract":"Fentanyl is a synthetic opioid with higher potency compared to morphine and heroin, making it an essential drug for pain management and also an abused drug. Beyond fentanyl, derivatives, such as o-fluoro fentanyl and furanyl fentanyl, also possess similar potency and present a significant risk of misuse, but without medical utility. A major challenge for law enforcement is detecting fentanyl and its analogues in their degraded forms. While the degradation fragments of fentanyl are well- known, those of its analogues are not as well studied. Here, we investigated the thermal degradation pathways of fentanyl analogues using extensive ab initio molecular dynamics simulations combined with enhanced sampling techniques, including multiple walker metadynamics. We calculated the free energy profiles for each bond previously identified as a potential degradation site to map out the thermodynamic driving forces. Additionally, we estimated the forward attempt rate of each bond degradation reaction to gain insights into the kinetics of those degradation processes. Our results showed that, despite high similarity in structure, the bond breaking pathways differ for the analogues compared with fentanyl. We also observe that traditional force fields with fixed charges are insufficient for studies of fentanyl and its analogues due to polarizability of the electronic structure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"25 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813637","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}
Vinylperoxy radicals were produced in a pulsed supersonic jet by discharging a gas mixture of vinyl bromide and molecular oxygen largely diluted in the Ar or Ne buffer gas. Two conformers of the radical, s-trans and s-cis, were detected through their pure rotational transitions via Fourier-transform microwave spectroscopy. Fine and hyperfine components in the observed spectra were fully assigned and analyzed to determine precise molecular constants for each conformer. The Fermi coupling constants determined for the –CH2 protons indicate that non-negligible unpaired spin density is located on the terminal carbon atom, although the radical is generally considered as the oxygen-centered radical. The intensities of the observed spectra are much weaker than expected, probably because most of nascent vinylperoxy radicals formed by the association of the vinyl radical and O2 promptly dissociate either to the vinoxy radical and atomic oxygen, or to formaldehyde and the formyl radical, even under jet-cooled conditions.
{"title":"Microwave spectroscopy of the vinylperoxy radical, CH2CHOO","authors":"Masakazu Nakajima, Yasuki Endo","doi":"10.1039/d5cp00649j","DOIUrl":"https://doi.org/10.1039/d5cp00649j","url":null,"abstract":"Vinylperoxy radicals were produced in a pulsed supersonic jet by discharging a gas mixture of vinyl bromide and molecular oxygen largely diluted in the Ar or Ne buffer gas. Two conformers of the radical, s-<em>trans</em> and s-<em>cis</em>, were detected through their pure rotational transitions <em>via</em> Fourier-transform microwave spectroscopy. Fine and hyperfine components in the observed spectra were fully assigned and analyzed to determine precise molecular constants for each conformer. The Fermi coupling constants determined for the –CH<small><sub>2</sub></small> protons indicate that non-negligible unpaired spin density is located on the terminal carbon atom, although the radical is generally considered as the oxygen-centered radical. The intensities of the observed spectra are much weaker than expected, probably because most of nascent vinylperoxy radicals formed by the association of the vinyl radical and O<small><sub>2</sub></small> promptly dissociate either to the vinoxy radical and atomic oxygen, or to formaldehyde and the formyl radical, even under jet-cooled conditions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"108 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813640","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}
Utilizing deep neural network potentials within molecular dynamics simulations, this research uncovers insights into fullerene formation and interconversion, particularly during the cooling annealing process. Our deep learning-enhanced approach effectively models the generation of fullerenes from C2 units in carbon vapor, highlighting the critical role of carbon density in structuring outcomes, also in a primary iron-carbon system. This study provides differences of molecular dynamics simulations for fullerene generation and also demonstrates the potential of deep learning in investigating complex carbon structures, paving the way for further investigations into fullerene family.
{"title":"Unveiling Fullerene Formation and Interconversion through Deep Learning Molecular Dynamics","authors":"Yanbo Han, Mengyang Li, Masahiro Ehara, Xiang Zhao","doi":"10.1039/d5cp00837a","DOIUrl":"https://doi.org/10.1039/d5cp00837a","url":null,"abstract":"Utilizing deep neural network potentials within molecular dynamics simulations, this research uncovers insights into fullerene formation and interconversion, particularly during the cooling annealing process. Our deep learning-enhanced approach effectively models the generation of fullerenes from C2 units in carbon vapor, highlighting the critical role of carbon density in structuring outcomes, also in a primary iron-carbon system. This study provides differences of molecular dynamics simulations for fullerene generation and also demonstrates the potential of deep learning in investigating complex carbon structures, paving the way for further investigations into fullerene family.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"241 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813737","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 dissociation of water on TiO2 surfaces, marked by the presence of TiOH groups, is pivotal for environmental and energy applications involving TiO2. Yet characterizing these surface groups has remained a challenge. Here, we employ in situ sum-frequency vibrational spectroscopy (SFVS) to unveil the vibrational signatures of surface TiOH and undercoordinated Ti-O groups in the Ti-O vibrational frequency range, offering a clear structural indicator of TiO2 hydroxylation. Our findings confirm the spontaneous dissociation of water molecules on TiO2 surfaces, a process significantly enhanced by structural defects such as oxygen vacancies. Through methanol titration experiments, we gain molecular-level insights into the adsorption/desorption dynamics, estimating a ~70% TiOH coverage on amorphous TiO2 under ambient conditions. This work not only deepens our understanding of TiO2/water interactions but also lays the groundwork for future SFVS investigations into these interfaces.
{"title":"Auto-dissociation of atmospheric water on TiO2: insights from sum-frequency spectroscopy of Ti-O vibrations","authors":"Hui Li, Wenqi Zheng, Xinyi Liu, Jiashi Li, Lianbing Wen, Fujie Tang, Weitao Liu","doi":"10.1039/d5cp00400d","DOIUrl":"https://doi.org/10.1039/d5cp00400d","url":null,"abstract":"The dissociation of water on TiO2 surfaces, marked by the presence of TiOH groups, is pivotal for environmental and energy applications involving TiO2. Yet characterizing these surface groups has remained a challenge. Here, we employ in situ sum-frequency vibrational spectroscopy (SFVS) to unveil the vibrational signatures of surface TiOH and undercoordinated Ti-O groups in the Ti-O vibrational frequency range, offering a clear structural indicator of TiO2 hydroxylation. Our findings confirm the spontaneous dissociation of water molecules on TiO2 surfaces, a process significantly enhanced by structural defects such as oxygen vacancies. Through methanol titration experiments, we gain molecular-level insights into the adsorption/desorption dynamics, estimating a ~70% TiOH coverage on amorphous TiO2 under ambient conditions. This work not only deepens our understanding of TiO2/water interactions but also lays the groundwork for future SFVS investigations into these interfaces.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"183 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813727","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}
Ali Keshavarz Mohammadian, Negar Ashari Astani, Farzaneh Shayeganfar
Hole transporting materials (HTMs) play a crucial role in the performance and stability of perovskite solar cells (PSCs). The interaction of HTMs with water significantly affects the overall stability and efficiency of these devices. Hydrophilic HTMs or those lacking adequate water resistance can absorb moisture, leading to degradation of both the HTM and the perovskite layer. In this study, we employed a proof-of-principle approach to investigate the effect of various chemical modifications on a promising HTM candidate, 8,11-bis(4-(N,N-bis(4-methoxyphenyl)amino)-1-phenyl)-dithieno [1,2- b:4,3-b’]phenazine (TQ4). Using molecular dynamics simulations, we examined the collective be- havior of chemically modified TQ4 molecules in the presence of water at different concentrations. To ensure that enhanced water resistance did not compromise the desirable electronic properties of the HTM, we analyzed both the individual and collective electronic structures of the HTM molecule and its molecular crystal. Additionally, we calculated the charge transport rate in different directions within the HTM crystal using Marcus theory. Our findings indicate that chemical modifications at the periphery of TQ4, particularly the symmetric addition of two F-chains, result in the optimal combination of electronic, crystal structure, and water-resistant properties. HOMO shape analysis reveals that the HOMO does not extend onto the added F-chains, reducing the maximum pre- dicted hole mobility relative to TQ4 by an order of magnitude. Despite this, a hole mobility of 2.8×10−4cm2V−1s−1 is successfully achieved for all designed HTMs, reflecting a compromise be- tween stability and charge transport. This atomistic insight into the collective behavior of chemically modified HTMs and its effect on hole transport pathways paves the way for designing more effective HTMs for PSC applications.
{"title":"Computational Design of Dopant-Free Hole Transporting Materials: Achieving an Optimal Balance Between Water Stability and Charge Transport","authors":"Ali Keshavarz Mohammadian, Negar Ashari Astani, Farzaneh Shayeganfar","doi":"10.1039/d5cp00082c","DOIUrl":"https://doi.org/10.1039/d5cp00082c","url":null,"abstract":"Hole transporting materials (HTMs) play a crucial role in the performance and stability of perovskite solar cells (PSCs). The interaction of HTMs with water significantly affects the overall stability and efficiency of these devices. Hydrophilic HTMs or those lacking adequate water resistance can absorb moisture, leading to degradation of both the HTM and the perovskite layer. In this study, we employed a proof-of-principle approach to investigate the effect of various chemical modifications on a promising HTM candidate, 8,11-bis(4-(N,N-bis(4-methoxyphenyl)amino)-1-phenyl)-dithieno [1,2- b:4,3-b’]phenazine (TQ4). Using molecular dynamics simulations, we examined the collective be- havior of chemically modified TQ4 molecules in the presence of water at different concentrations. To ensure that enhanced water resistance did not compromise the desirable electronic properties of the HTM, we analyzed both the individual and collective electronic structures of the HTM molecule and its molecular crystal. Additionally, we calculated the charge transport rate in different directions within the HTM crystal using Marcus theory. Our findings indicate that chemical modifications at the periphery of TQ4, particularly the symmetric addition of two F-chains, result in the optimal combination of electronic, crystal structure, and water-resistant properties. HOMO shape analysis reveals that the HOMO does not extend onto the added F-chains, reducing the maximum pre- dicted hole mobility relative to TQ4 by an order of magnitude. Despite this, a hole mobility of 2.8×10−4cm2V−1s−1 is successfully achieved for all designed HTMs, reflecting a compromise be- tween stability and charge transport. This atomistic insight into the collective behavior of chemically modified HTMs and its effect on hole transport pathways paves the way for designing more effective HTMs for PSC applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806213","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}
Jiaqi Zhang, Jiaxin Jiang, Hongyan Guo, Xiaowei Sheng, Weiyi Wang, Zhiwen Zhuo, Ning Lu
The development of high-comprehensive-performance cathode materials is significant and urgent for ion battery systems. Based on density functional theory methods, we systematically expand and investigate a porous and van der Waals layered bulk structure of carbon nitride as a versatile cathode material for varied ion batteries. The calculated results indicate that the layered bulk carbon nitride structure is a semiconductor material with good thermal stability. The structure has high-density one-dimensional transport channels for fast K/Na/Ca ions migration with low activation energy barriers of only 0.125, 0.281, and 0.296 eV, respectively. The theoretical specific capacity, open-circuit voltage, and energy density can reach 137, 150, and 273 mAh·g-1, 3.788-3.614, 3.251-3.037, and 3.376-2.821 V, and 506.1, 470.8, and 847.3 Wh·kg-1 for K, Na and Ca ion, respectively. Compared to common cathode materials, the layered carbon nitride possesses significant advantages such as fast ion, high energy density, low cost, and environmental friendliness.
{"title":"Layered carbon nitride bulk as a versatile cathode material for fast ion batteries","authors":"Jiaqi Zhang, Jiaxin Jiang, Hongyan Guo, Xiaowei Sheng, Weiyi Wang, Zhiwen Zhuo, Ning Lu","doi":"10.1039/d5cp00187k","DOIUrl":"https://doi.org/10.1039/d5cp00187k","url":null,"abstract":"The development of high-comprehensive-performance cathode materials is significant and urgent for ion battery systems. Based on density functional theory methods, we systematically expand and investigate a porous and van der Waals layered bulk structure of carbon nitride as a versatile cathode material for varied ion batteries. The calculated results indicate that the layered bulk carbon nitride structure is a semiconductor material with good thermal stability. The structure has high-density one-dimensional transport channels for fast K/Na/Ca ions migration with low activation energy barriers of only 0.125, 0.281, and 0.296 eV, respectively. The theoretical specific capacity, open-circuit voltage, and energy density can reach 137, 150, and 273 mAh·g-1, 3.788-3.614, 3.251-3.037, and 3.376-2.821 V, and 506.1, 470.8, and 847.3 Wh·kg-1 for K, Na and Ca ion, respectively. Compared to common cathode materials, the layered carbon nitride possesses significant advantages such as fast ion, high energy density, low cost, and environmental friendliness.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"93 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806217","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：