Pub Date : 2025-01-27DOI: 10.1021/acs.jpclett.4c02956
Peter Johansson, Mikael Käll, Hana Šípová-Jungová
Functional gold nanoparticles have emerged as a cornerstone in targeted drug delivery, imaging, and biosensing. Their stability, distribution, and overall performance in biological systems are largely determined by their interactions with molecules in biological fluids as well as the biomolecular layers they acquire in complex environments. However, real-time tracking of how biomolecules attach to colloidal nanoparticles, a critical aspect for optimizing nanoparticle function, has proven to be experimentally challenging. To address this issue, we present a depolarized forward light scattering (DFLS) method that measures rotational relaxation constants. In DFLS, optically anisotropic nanoparticles are illuminated with linearly polarized light and the forward light scattering is analyzed in a cross-polarized configuration. We demonstrate the application of DFLS to characterize various functional coatings, analyze biomolecular binding kinetics to gold nanoparticles, and determine specific protein adsorption affinity constants. Our results indicate that DFLS offers a powerful approach to studying nanoparticle-biomolecule interactions in complex environments such as bodily fluids, thereby opening new pathways for advancements in nanomedicine and the optimization of nanoparticle-based drug delivery systems.
{"title":"Depolarized Forward Light Scattering for Subnanometer Precision in Biomolecular Layer Analysis on Gold Nanorods","authors":"Peter Johansson, Mikael Käll, Hana Šípová-Jungová","doi":"10.1021/acs.jpclett.4c02956","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02956","url":null,"abstract":"Functional gold nanoparticles have emerged as a cornerstone in targeted drug delivery, imaging, and biosensing. Their stability, distribution, and overall performance in biological systems are largely determined by their interactions with molecules in biological fluids as well as the biomolecular layers they acquire in complex environments. However, real-time tracking of how biomolecules attach to colloidal nanoparticles, a critical aspect for optimizing nanoparticle function, has proven to be experimentally challenging. To address this issue, we present a depolarized forward light scattering (DFLS) method that measures rotational relaxation constants. In DFLS, optically anisotropic nanoparticles are illuminated with linearly polarized light and the forward light scattering is analyzed in a cross-polarized configuration. We demonstrate the application of DFLS to characterize various functional coatings, analyze biomolecular binding kinetics to gold nanoparticles, and determine specific protein adsorption affinity constants. Our results indicate that DFLS offers a powerful approach to studying nanoparticle-biomolecule interactions in complex environments such as bodily fluids, thereby opening new pathways for advancements in nanomedicine and the optimization of nanoparticle-based drug delivery systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Ni–N(His) coordination bond, formed between the nickel ion and histidine residues, is essential for recombinant protein purification, especially in Ni-NTA-based systems for selectively binding polyhistidine-tagged (Histag) proteins. While previous studies have explored its bond strength in a synthetic Ni-NTA-Histag system, the influence of the surrounding protein structure remains less understood. In this study, we used atomic force microscopy-based single-molecule force spectroscopy (AFM-SMFS) to quantify the Ni–N(His) bond strength in calprotectin, a biologically relevant protein system. Our results demonstrate that the Ni–N(His) bond in protein exhibits a rupture force of ∼56 pN. Notably, kinetic analysis revealed a significantly lower off-rate compared to the synthetic system, suggesting that the protein environment plays a crucial role in stabilizing the bond. Moreover, we found that the bond is less susceptible to displacement by competing agents, such as imidazole, and experiences only a modest decrease in stability under acidic conditions, compared to the dramatic weakening seen in a synthetic system. These findings highlight the role of protein structure in protecting the mechanical and kinetic stability of the Ni–N(His) bond, offering insights into understanding the metal–ligand interactions in proteins in general.
{"title":"Calprotectin’s Protein Structure Shields Ni–N(His) Bonds from Competing Agents","authors":"Zhuojian Lu, Jingyuan Nie, Ziling Wang, Ziyi Wang, Panke Zhang, Yajun Jiang, Peng Zheng","doi":"10.1021/acs.jpclett.4c03229","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03229","url":null,"abstract":"The Ni–N(His) coordination bond, formed between the nickel ion and histidine residues, is essential for recombinant protein purification, especially in Ni-NTA-based systems for selectively binding polyhistidine-tagged (Histag) proteins. While previous studies have explored its bond strength in a synthetic Ni-NTA-Histag system, the influence of the surrounding protein structure remains less understood. In this study, we used atomic force microscopy-based single-molecule force spectroscopy (AFM-SMFS) to quantify the Ni–N(His) bond strength in calprotectin, a biologically relevant protein system. Our results demonstrate that the Ni–N(His) bond in protein exhibits a rupture force of ∼56 pN. Notably, kinetic analysis revealed a significantly lower off-rate compared to the synthetic system, suggesting that the protein environment plays a crucial role in stabilizing the bond. Moreover, we found that the bond is less susceptible to displacement by competing agents, such as imidazole, and experiences only a modest decrease in stability under acidic conditions, compared to the dramatic weakening seen in a synthetic system. These findings highlight the role of protein structure in protecting the mechanical and kinetic stability of the Ni–N(His) bond, offering insights into understanding the metal–ligand interactions in proteins in general.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-27DOI: 10.1021/acs.jpclett.4c03410
Shuxian Li, Wei Ge, Xiaoyu Huang, Hong Du, Fu Wang
Gold nanoclusters (Au NCs) protected by molecular ligands represent a new class of second-generation near-infrared (NIR-II) luminescent materials that have been widely studied. However, the photoluminescence efficiencies of most NIR-II emitting Au NCs in aqueous solution are generally lower than 0.2%, and to fully exploit the advantages of AuNCs in the NIR-II region, improving their photoluminescence efficiency has become an urgent need. Considering the holistic nature of the core–shell structure of Au NCs, herein, we propose a synergistic intramolecular charge transfer (ICT) strategy to enhance the luminescence. The NIR-II fluorescence quantum yield of Au NCs was increased 6-fold to 5.59% by the synergistic effect of heteroatomic copper doping and ligand p-MBA deprotonation. Experimental characterization results show that the strong p-π conjugation between d10 metal and the deprotonated p-MBA enhances the charge transfer between the metal core and ligand. The synergistic ICT process strongly suppressed the nonradiative process, thereby enhancing the emission intensity. Our findings provide a facile method for understanding the integrity of the core–shell structure of Au NCs and regulating their photoluminescence properties.
{"title":"Synergistic Intramolecular Charge Transfer Promotes Au Nanoclusters with Enhanced NIR-II Photoluminescence","authors":"Shuxian Li, Wei Ge, Xiaoyu Huang, Hong Du, Fu Wang","doi":"10.1021/acs.jpclett.4c03410","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03410","url":null,"abstract":"Gold nanoclusters (Au NCs) protected by molecular ligands represent a new class of second-generation near-infrared (NIR-II) luminescent materials that have been widely studied. However, the photoluminescence efficiencies of most NIR-II emitting Au NCs in aqueous solution are generally lower than 0.2%, and to fully exploit the advantages of AuNCs in the NIR-II region, improving their photoluminescence efficiency has become an urgent need. Considering the holistic nature of the core–shell structure of Au NCs, herein, we propose a synergistic intramolecular charge transfer (ICT) strategy to enhance the luminescence. The NIR-II fluorescence quantum yield of Au NCs was increased 6-fold to 5.59% by the synergistic effect of heteroatomic copper doping and ligand p-MBA deprotonation. Experimental characterization results show that the strong p-π conjugation between d<sub>10</sub> metal and the deprotonated p-MBA enhances the charge transfer between the metal core and ligand. The synergistic ICT process strongly suppressed the nonradiative process, thereby enhancing the emission intensity. Our findings provide a facile method for understanding the integrity of the core–shell structure of Au NCs and regulating their photoluminescence properties.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"10 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, we study the plexciton in the far-ultraviolet region formed between indium nanoclusters and water molecules. The indium clusters are fabricated on graphene under ultrahigh vacuum conditions and show a strong localized surface plasmon polariton (LSP) absorption band at 6–7 eV. Adsorption of water molecules onto the clusters at 115 K induces a band splitting larger than 1 eV, indicating a strong coupling between the LSP and water 4a1 ← 1b1 transition. The spectral evolution as a function of the water coverage is revealed, enabling the determination of the decay length of the plexciton collective effect to be ∼8 nm.
{"title":"Far-Ultraviolet Plexciton Formation in Water-Covered Indium Clusters","authors":"Naoki Nagatsuka, Ryoto Matsuguchi, Kazuya Watanabe, Takanori Koitaya, Daiki Yamamoto, Hiroshi Okuyama, Tomokazu Yasuike","doi":"10.1021/acs.jpclett.5c00001","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00001","url":null,"abstract":"In this work, we study the plexciton in the far-ultraviolet region formed between indium nanoclusters and water molecules. The indium clusters are fabricated on graphene under ultrahigh vacuum conditions and show a strong localized surface plasmon polariton (LSP) absorption band at 6–7 eV. Adsorption of water molecules onto the clusters at 115 K induces a band splitting larger than 1 eV, indicating a strong coupling between the LSP and water 4a<sub>1</sub> ← 1b<sub>1</sub> transition. The spectral evolution as a function of the water coverage is revealed, enabling the determination of the decay length of the plexciton collective effect to be ∼8 nm.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"47 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-27DOI: 10.1021/acs.jpclett.4c03425
Huizhen Li, Kang Li, Wenyu Hu, Jianyuan Zhao, Tong Su, Jielin Yang, Yiming Chen, Kuo Yang, Mei Du, Zhe Li, Weiwei Zhao
We have systematically studied the electromagnetic transport properties of PbTe thin films under gate voltage modulation. The system demonstrates pronounced electron–electron interactions exclusively within the gate voltage range where only hole carriers are present. Furthermore, the Berry phase is utilized to qualitatively elucidate the transition between weak antilocalization (WAL) and weak localization (WL) through the regulation of gate voltage and temperature. Using the three-resistor model, we have effectively explained the correlation between the characteristic temperature of the R–T curve, the coexistence of electron–hole carriers, and the nonmonotonic temperature dependence of negative magnetoresistance (NMR), consistently indicating that complex magnetotransport phenomena are caused by microscopic disorder. Our research findings open up new avenues for exploring and manipulating the magnetotransport properties of PbTe thin films.
{"title":"Weak Antilocalization and Negative Magnetoresistance of the Gate-Tunable PbTe Thin Films","authors":"Huizhen Li, Kang Li, Wenyu Hu, Jianyuan Zhao, Tong Su, Jielin Yang, Yiming Chen, Kuo Yang, Mei Du, Zhe Li, Weiwei Zhao","doi":"10.1021/acs.jpclett.4c03425","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03425","url":null,"abstract":"We have systematically studied the electromagnetic transport properties of PbTe thin films under gate voltage modulation. The system demonstrates pronounced electron–electron interactions exclusively within the gate voltage range where only hole carriers are present. Furthermore, the Berry phase is utilized to qualitatively elucidate the transition between weak antilocalization (WAL) and weak localization (WL) through the regulation of gate voltage and temperature. Using the three-resistor model, we have effectively explained the correlation between the characteristic temperature of the <i>R</i>–<i>T</i> curve, the coexistence of electron–hole carriers, and the nonmonotonic temperature dependence of negative magnetoresistance (NMR), consistently indicating that complex magnetotransport phenomena are caused by microscopic disorder. Our research findings open up new avenues for exploring and manipulating the magnetotransport properties of PbTe thin films.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"21 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044658","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-27DOI: 10.1021/acs.jpclett.4c03396
Vincent J. Esposito, Piero Ferrari, C. Zachary Palmer, Christiaan Boersma, Alessandra Candian, Ryan C. Fortenberry, Wybren Jan Buma, Alexander G. G. M. Tielens
The CN stretch frequency of neutral, gas-phase 9-cyanoanthracene is 2207 cm–1 (4.531 μm) based on high-resolution infrared absorption experiments coupled with a new hybrid anharmonic quantum chemical methodology. A broad band (full-width at half-maximum of 47 cm–1) is observed and assigned to multiple transitions, including the CN stretch fundamental and various combination bands that gather intensity from strong anharmonic coupling with the bright CN stretch. The new hybrid computational approach utilizes the harmonic force constants from the double-hybrid rev-DSDPBEP86 functional that includes MP2 electron correlation, and the cubic and quartic force constants from the B3LYP density functional. In combination, this method computes a band center of 2207 cm–1 for 9-cyanoanthracene, a direct match with experiment. Further, the hybrid method produces a difference of less than 1 cm–1 for the two isomers of cyanonaphthalene and cyanobenzene. As shown from comparison with CCSD(T)-F12b anharmonic frequency computations of cyanobenzene, inclusion of electron correlation is required to properly characterize the electronic structure of the highly electron withdrawing CN group on polycyclic aromatic hydrocarbons. In agreement with earlier studies, computation of the CN stretch of 14 small CN-PAHs produces a narrow (∼20 cm–1) band from 2207–2229 cm–1 (4.53–4.48 μm). The remainder of the spectrum below 2000 cm–1 and from 3000–3120 cm–1 shows good agreement between experiment and the hybrid theory with a mean absolute error of 16 and 14 cm–1, respectively.
{"title":"Pinpointing the CN Stretch Frequency of Neutral Cyano-Polycyclic Aromatic Hydrocarbons: A Laboratory and Quantum Chemical Spectroscopic Study of 9-Cyanoanthracene","authors":"Vincent J. Esposito, Piero Ferrari, C. Zachary Palmer, Christiaan Boersma, Alessandra Candian, Ryan C. Fortenberry, Wybren Jan Buma, Alexander G. G. M. Tielens","doi":"10.1021/acs.jpclett.4c03396","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03396","url":null,"abstract":"The CN stretch frequency of neutral, gas-phase 9-cyanoanthracene is 2207 cm<sup>–1</sup> (4.531 μm) based on high-resolution infrared absorption experiments coupled with a new hybrid anharmonic quantum chemical methodology. A broad band (full-width at half-maximum of 47 cm<sup>–1</sup>) is observed and assigned to multiple transitions, including the CN stretch fundamental and various combination bands that gather intensity from strong anharmonic coupling with the bright CN stretch. The new hybrid computational approach utilizes the harmonic force constants from the double-hybrid rev-DSDPBEP86 functional that includes MP2 electron correlation, and the cubic and quartic force constants from the B3LYP density functional. In combination, this method computes a band center of 2207 cm<sup>–1</sup> for 9-cyanoanthracene, a direct match with experiment. Further, the hybrid method produces a difference of less than 1 cm<sup>–1</sup> for the two isomers of cyanonaphthalene and cyanobenzene. As shown from comparison with CCSD(T)-F12b anharmonic frequency computations of cyanobenzene, inclusion of electron correlation is required to properly characterize the electronic structure of the highly electron withdrawing CN group on polycyclic aromatic hydrocarbons. In agreement with earlier studies, computation of the CN stretch of 14 small CN-PAHs produces a narrow (∼20 cm<sup>–1</sup>) band from 2207–2229 cm<sup>–1</sup> (4.53–4.48 μm). The remainder of the spectrum below 2000 cm<sup>–1</sup> and from 3000–3120 cm<sup>–1</sup> shows good agreement between experiment and the hybrid theory with a mean absolute error of 16 and 14 cm<sup>–1</sup>, respectively.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-26DOI: 10.1021/acs.jpclett.4c03299
Yaran Cheng, Jiahao Wang, Yangyang Shen, Haixing Li
Amines are one of the most ubiquitous functional groups in molecular junctions; however, the exact regulation of the charge transport through the protonation state of an amine group in the junction backbone remains elusive. We address this question here by designing a diphenylamine molecular backbone and experimentally investigating how protonation of the central amine group affects the charge transport. Our ultraviolet–visible spectroscopy measurements demonstrate the protonation reaction of the diphenylamine compound in the presence of either trifluoroacetic acid or HCl, and we observe a consistent trend of a modestly increased conductance for diphenylamine in the presence of acid, indicating that a protonated amine group in a diphenylamine backbone slightly enhances the electron conduction. We further investigate the charge transport across diphenylamine under a series of applied tip bias voltages between −0.9 to 0.9 V in an electrochemical environment in the absence and presence of acid for determining the frontier molecular orbital alignment with the Fermi level and the coupling coefficient between the molecule and the electrodes. Our finding shows that the highest occupied molecular orbital (HOMO) is the dominating transport channel of the diphenylamine junction, and a modest conductance increase is an outcome of the HOMO resonance energy moving closer to the Fermi level upon protonation of the amine.
{"title":"Protonation-Independent Charge Transport Across Diphenylamine Single-Molecule Junctions","authors":"Yaran Cheng, Jiahao Wang, Yangyang Shen, Haixing Li","doi":"10.1021/acs.jpclett.4c03299","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03299","url":null,"abstract":"Amines are one of the most ubiquitous functional groups in molecular junctions; however, the exact regulation of the charge transport through the protonation state of an amine group in the junction backbone remains elusive. We address this question here by designing a diphenylamine molecular backbone and experimentally investigating how protonation of the central amine group affects the charge transport. Our ultraviolet–visible spectroscopy measurements demonstrate the protonation reaction of the diphenylamine compound in the presence of either trifluoroacetic acid or HCl, and we observe a consistent trend of a modestly increased conductance for diphenylamine in the presence of acid, indicating that a protonated amine group in a diphenylamine backbone slightly enhances the electron conduction. We further investigate the charge transport across diphenylamine under a series of applied tip bias voltages between −0.9 to 0.9 V in an electrochemical environment in the absence and presence of acid for determining the frontier molecular orbital alignment with the Fermi level and the coupling coefficient between the molecule and the electrodes. Our finding shows that the highest occupied molecular orbital (HOMO) is the dominating transport channel of the diphenylamine junction, and a modest conductance increase is an outcome of the HOMO resonance energy moving closer to the Fermi level upon protonation of the amine.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"150 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-26DOI: 10.1021/acs.jpclett.4c03358
Bing Yang, Bo Cai, Junmin Xia, Yi Liu, Yangzhi Ma, Jibin Zhang, Lihui Liu, Kun Cao, Wei Shen, Siyu Chen, Shufen Chen
Halide perovskite optoelectronic devices achieve high energy conversion efficiencies. However, their efficiency decreases significantly with an increase in temperature. This decline is likely caused by changes in nonradiative recombination and electron–phonon coupling, which remain underexplored. When the perovskite lattice temperature increases, anharmonicity induces energy level fluctuation and band gap narrowing by modulating electron–phonon interactions. As lattice vibrations intensify, high-frequency phonons progressively dominate the carrier dynamic processes in halide perovskites, thereby strengthening the coupling between the electronic subsystem and high-frequency phonons. The increased overlap of electron wave functions strengthens non-adiabatic coupling, thereby accelerating the nonradiative recombination process. On the basis of these findings, we propose the introduction of appropriate band gap materials and heavy atoms at the B-site and X-site to modulate electron–phonon coupling, thereby mitigating nonradiative recombination and enhancing halide perovskite solar cell performance.
{"title":"Reducing Nonradiative Recombination in Halide Perovskites through Appropriate Band Gaps and Heavy Atomic Masses","authors":"Bing Yang, Bo Cai, Junmin Xia, Yi Liu, Yangzhi Ma, Jibin Zhang, Lihui Liu, Kun Cao, Wei Shen, Siyu Chen, Shufen Chen","doi":"10.1021/acs.jpclett.4c03358","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03358","url":null,"abstract":"Halide perovskite optoelectronic devices achieve high energy conversion efficiencies. However, their efficiency decreases significantly with an increase in temperature. This decline is likely caused by changes in nonradiative recombination and electron–phonon coupling, which remain underexplored. When the perovskite lattice temperature increases, anharmonicity induces energy level fluctuation and band gap narrowing by modulating electron–phonon interactions. As lattice vibrations intensify, high-frequency phonons progressively dominate the carrier dynamic processes in halide perovskites, thereby strengthening the coupling between the electronic subsystem and high-frequency phonons. The increased overlap of electron wave functions strengthens non-adiabatic coupling, thereby accelerating the nonradiative recombination process. On the basis of these findings, we propose the introduction of appropriate band gap materials and heavy atoms at the B-site and X-site to modulate electron–phonon coupling, thereby mitigating nonradiative recombination and enhancing halide perovskite solar cell performance.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lead-free tin halide perovskite solar cells (TPSCs) have recently made significant progress in power conversion efficiency (PCE). However, the presence of mismatched energy levels and weak interlayer interactions between the electron transport materials (ETMs) and tin perovskites has limited the achievable PCE. Here, a new fluorinated fullerene derivative, C60-FTPA (F12), was designed and synthesized to construct a binary ETM with C60-ETPA (F6) reported in our group, resulting in a reduction in defects and improved molecular structure ordering. Furthermore, the binary ETM exhibited a stronger interaction with the tin perovskite and delivered a PCE up to 11.93%.
{"title":"Enhanced Interlayer Interactions in Tin Halide Perovskite Solar Cells with a Fluorinated Fullerene Derivative","authors":"Cheng Wu, Miao Zhang, Mingyu Yin, Jie Luo, Liming Ding, Feng Hao","doi":"10.1021/acs.jpclett.4c03710","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03710","url":null,"abstract":"Lead-free tin halide perovskite solar cells (TPSCs) have recently made significant progress in power conversion efficiency (PCE). However, the presence of mismatched energy levels and weak interlayer interactions between the electron transport materials (ETMs) and tin perovskites has limited the achievable PCE. Here, a new fluorinated fullerene derivative, C<sub>60</sub>-FTPA (F12), was designed and synthesized to construct a binary ETM with C<sub>60</sub>-ETPA (F6) reported in our group, resulting in a reduction in defects and improved molecular structure ordering. Furthermore, the binary ETM exhibited a stronger interaction with the tin perovskite and delivered a PCE up to 11.93%.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"38 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1021/acs.jpclett.4c03372
Oleg A. Igoshin, Anatoly B. Kolomeisky, Dmitrii E. Makarov
Continuous production of entropy and the corresponding energy dissipation is a defining characteristic of nonequilibrium systems. When a system’s full chemical kinetic description is known, its entropy production rate can be computed from the microscopic rate constants. However, such a calculation typically underestimates energy dissipation when the states of the underlying system are mesoscopic, i.e., when they combine multiple microscopic states, a situation typical in experimental measurements with finite resolution. It is unknown whether there is a mesoscopic coarse-graining procedure that produces fewer states but allows for precise entropy production calculations. Here we develop a universal coarse-graining procedure that we call “trimming”, in which microscopic states of the original Markov network are progressively eliminated but the fluxes between remaining states are exactly preserved. We demonstrate that this procedure also preserves entropy production as long as no dissipative loops are eliminated. We apply our method to several examples illustrating how trimming affects local network topology.
{"title":"Coarse-Graining Chemical Networks by Trimming to Preserve Energy Dissipation","authors":"Oleg A. Igoshin, Anatoly B. Kolomeisky, Dmitrii E. Makarov","doi":"10.1021/acs.jpclett.4c03372","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03372","url":null,"abstract":"Continuous production of entropy and the corresponding energy dissipation is a defining characteristic of nonequilibrium systems. When a system’s full chemical kinetic description is known, its entropy production rate can be computed from the microscopic rate constants. However, such a calculation typically underestimates energy dissipation when the states of the underlying system are mesoscopic, i.e., when they combine multiple microscopic states, a situation typical in experimental measurements with finite resolution. It is unknown whether there is a mesoscopic coarse-graining procedure that produces fewer states but allows for precise entropy production calculations. Here we develop a universal coarse-graining procedure that we call “trimming”, in which microscopic states of the original Markov network are progressively eliminated but the fluxes between remaining states are exactly preserved. We demonstrate that this procedure also preserves entropy production as long as no dissipative loops are eliminated. We apply our method to several examples illustrating how trimming affects local network topology.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"22 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143030821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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