Pub Date : 2026-03-16DOI: 10.1021/acs.jpclett.5c04090
Xiang Sun, Zengkui Liu
Nonadiabatic dynamics in the condensed phase often involve correlated environments shared by multiple electronic states, challenging the traditional isolated bath assumption. We investigate these effects using the multistate harmonic (MSH) model and atomistic Hamiltonian applied to photoinduced charge transfer in a trimer consisting of a methylperylene donor and two tetracyanoethylene acceptors dissolved in a polar solvent. We propose a geometric metric based on the angular relationship of reorganization energies between transitions sharing an initial state to quantify bath correlation. Our analysis identifies distinct regimes: a correlated bath where synchronized energy gap fluctuations facilitate competing reactions, and an anticorrelated bath where fluctuations favoring one reaction suppress the other. These energetic correlations are modulated by molecular conformation and charge distribution, specifically through changes in dipole moments and solvent-accessible surface area. This study provides a connection between the energetic perspective of environmental correlations and the molecular details governing nonadiabatic dynamics in polar solvents.
{"title":"Molecular Origin of Correlated Bath Effects in Photoinduced Charge Transfer Dynamics in Polar Solvents","authors":"Xiang Sun, Zengkui Liu","doi":"10.1021/acs.jpclett.5c04090","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04090","url":null,"abstract":"Nonadiabatic dynamics in the condensed phase often involve correlated environments shared by multiple electronic states, challenging the traditional isolated bath assumption. We investigate these effects using the multistate harmonic (MSH) model and atomistic Hamiltonian applied to photoinduced charge transfer in a trimer consisting of a methylperylene donor and two tetracyanoethylene acceptors dissolved in a polar solvent. We propose a geometric metric based on the angular relationship of reorganization energies between transitions sharing an initial state to quantify bath correlation. Our analysis identifies distinct regimes: a correlated bath where synchronized energy gap fluctuations facilitate competing reactions, and an anticorrelated bath where fluctuations favoring one reaction suppress the other. These energetic correlations are modulated by molecular conformation and charge distribution, specifically through changes in dipole moments and solvent-accessible surface area. This study provides a connection between the energetic perspective of environmental correlations and the molecular details governing nonadiabatic dynamics in polar solvents.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461848","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}
Solid-state near-infrared (NIR)-to-visible triplet–triplet annihilation upconversion (TTA-UC) at the 1 μm edge is attractive for deep-tissue photonics and NIR energy harvesting but remains limited by sensitizer losses and restricted triplet transport in condensed media. Here we demonstrate porous poly(vinyl alcohol) (PVA)/rubrene films sensitized by spin-forbidden Ru complexes (DX1m–DX3m) with appreciable NIR absorption. Photon-flux-normalized action spectra show sensitizer-dependent red-edge response across the series, and DX3m affords quantifiable upconversion under 1000 nm femtosecond and 980 nm continuous-wave excitation, with detectable spectra to 1030 nm. Because spin-forbidden Ru sensitizers offer molecular tunability yet face threshold limitations from red-edge absorption and short triplet lifetimes, we examined what governs the operating thresholds in porous films. Transient kinetics indicate that excitation range is sensitizer-controlled, whereas thresholds are governed by triplet survival and encounter kinetics in porous domains rather than sensitizer-to-annihilator triplet–triplet energy transfer alone. These results establish a Ru-based route to 1-μm-class solid-state TTA-UC in polymer films.
{"title":"Spin-Forbidden Ru Sensitizers Enable 1 μm Excitation for Solid-State Triplet–Triplet Annihilation Photon Upconversion","authors":"Takumi Kinoshita, Takeshi Mori, Tomohiro Mori, Hiroshi Segawa, Hitoshi Saomoto","doi":"10.1021/acs.jpclett.6c00275","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00275","url":null,"abstract":"Solid-state near-infrared (NIR)-to-visible triplet–triplet annihilation upconversion (TTA-UC) at the 1 μm edge is attractive for deep-tissue photonics and NIR energy harvesting but remains limited by sensitizer losses and restricted triplet transport in condensed media. Here we demonstrate porous poly(vinyl alcohol) (PVA)/rubrene films sensitized by spin-forbidden Ru complexes (<b>DX1m</b>–<b>DX3m</b>) with appreciable NIR absorption. Photon-flux-normalized action spectra show sensitizer-dependent red-edge response across the series, and <b>DX3m</b> affords quantifiable upconversion under 1000 nm femtosecond and 980 nm continuous-wave excitation, with detectable spectra to 1030 nm. Because spin-forbidden Ru sensitizers offer molecular tunability yet face threshold limitations from red-edge absorption and short triplet lifetimes, we examined what governs the operating thresholds in porous films. Transient kinetics indicate that excitation range is sensitizer-controlled, whereas thresholds are governed by triplet survival and encounter kinetics in porous domains rather than sensitizer-to-annihilator triplet–triplet energy transfer alone. These results establish a Ru-based route to 1-μm-class solid-state TTA-UC in polymer films.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462060","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}
Single-molecule fluorescence blinking reflects reversible transitions between open emissive and closed nonemissive forms of rhodamine dyes. These transitions are strongly influenced by the local chemical environment. Here, we establish fluorescence blinking as a quantitative and interpretable readout of local physicochemical interactions. Hydroxymethyl silicon-rhodamine (HMSiR) was covalently linked to a series of short peptides designed to span defined electrostatic, hydrophobic, and hydrogen-bonding properties. Each peptide created a distinct microenvironment that modulated the spirocyclization equilibrium of the fluorophore. Blinking trajectories recorded under controlled conditions yielded descriptors such as on-state dwell times and state-transition statistics, which served as optical signatures of peptide-fluorophore interactions. Machine learning regression mapped these descriptors onto continuous physicochemical parameters, enabling accurate prediction of peptide net-charge, hydrophobicity, and hydrogen-bonding capacity. This work provides a direct connection between blinking dynamics and local physicochemical interactions, transforming stochastic fluorescence blinking into a mechanism-based chemical readout.
{"title":"Decoding Physicochemical Interactions Via Single-Molecule Fluorescence Blinking.","authors":"Yifeng Cheng,Jian Mao,Yue Li,Xintong Miao,Zheng Zhen,Guangyong Qin,Zhenzhen Feng,Xiaojuan Wang,Fang Huang,Hua He","doi":"10.1021/acs.jpclett.6c00001","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00001","url":null,"abstract":"Single-molecule fluorescence blinking reflects reversible transitions between open emissive and closed nonemissive forms of rhodamine dyes. These transitions are strongly influenced by the local chemical environment. Here, we establish fluorescence blinking as a quantitative and interpretable readout of local physicochemical interactions. Hydroxymethyl silicon-rhodamine (HMSiR) was covalently linked to a series of short peptides designed to span defined electrostatic, hydrophobic, and hydrogen-bonding properties. Each peptide created a distinct microenvironment that modulated the spirocyclization equilibrium of the fluorophore. Blinking trajectories recorded under controlled conditions yielded descriptors such as on-state dwell times and state-transition statistics, which served as optical signatures of peptide-fluorophore interactions. Machine learning regression mapped these descriptors onto continuous physicochemical parameters, enabling accurate prediction of peptide net-charge, hydrophobicity, and hydrogen-bonding capacity. This work provides a direct connection between blinking dynamics and local physicochemical interactions, transforming stochastic fluorescence blinking into a mechanism-based chemical readout.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"44 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461772","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 accurate modeling of the excited state landscapes in chiral materials requires an optimal balance between the description of their electronic structure and the influence of environmental effects. In this work, using a prototypical lead halide chiral perovskite, we show that embedding a chromophore in point charges has a beneficial effect in correcting the spurious representation of charge-transfer states arising from hybrid or semilocal approximations within density functional theory (DFT). Notably, the effect of the embedding also outperforms the benefits induced by the range-separated functionals. While the nature of the state remains similar, we demonstrate that the addition of point charges significantly decreases the electron–hole distance. The combination of hybrid functionals with embedding provides the best description of the experimental absorption spectrum, with the only exception being excitonic states that cannot be reproduced when considering a model constituted by a single cell.
{"title":"Optical Properties of Chiral Perovskites: The Role of Electrostatic Embedding in Correcting the Accuracy of Exchange-Correlation Functionals","authors":"Amina Alehyane,Elise Lognon,Mariagrazia Fortino,Eric Brémond,Florent Barbault,Adriana Pietropaolo,Antonio Monari","doi":"10.1021/acs.jpclett.6c00309","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00309","url":null,"abstract":"The accurate modeling of the excited state landscapes in chiral materials requires an optimal balance between the description of their electronic structure and the influence of environmental effects. In this work, using a prototypical lead halide chiral perovskite, we show that embedding a chromophore in point charges has a beneficial effect in correcting the spurious representation of charge-transfer states arising from hybrid or semilocal approximations within density functional theory (DFT). Notably, the effect of the embedding also outperforms the benefits induced by the range-separated functionals. While the nature of the state remains similar, we demonstrate that the addition of point charges significantly decreases the electron–hole distance. The combination of hybrid functionals with embedding provides the best description of the experimental absorption spectrum, with the only exception being excitonic states that cannot be reproduced when considering a model constituted by a single cell.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"308 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462265","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 : 2026-03-16DOI: 10.1021/acs.jpclett.5c04106
Premashis Manna,Mark A. Hix,Srijit Mukherjee,Alice R. Walker,Ralph Jimenez
Developing bright and photostable red fluorescent proteins (RFPs) is one of the “holy grails” of the protein engineering community. Despite several attempts, such fluorescent proteins (FPs) have remained elusive. One bottleneck to engineering next-generation RFPs is our lack of understanding of nonfluorescent or dark-state properties in such constructs. Here, we develop a theoretical and experimental framework that describes how photobleaching decays in FPs relate to dark-state conversion and ground-state recovery. Our systematic photophysical investigation of mCherry and mCherry-d, an RFP with enhanced dark-state behavior, showed the presence of photodestructive dark states in such FPs. Molecular dynamics simulations reveal enhanced fluctuation around the imidazolinone end of the chromophore in mCherry-d, potentially facilitating conversion to nonfluorescent states. Collectively, this work quantifies dark-state kinetics and provides insights into engineering dark states in RFPs to develop bright, yet photostable, molecular probes.
{"title":"Dark-State-Mediated Photobleaching in mCherry-Based Red Fluorescent Proteins","authors":"Premashis Manna,Mark A. Hix,Srijit Mukherjee,Alice R. Walker,Ralph Jimenez","doi":"10.1021/acs.jpclett.5c04106","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04106","url":null,"abstract":"Developing bright and photostable red fluorescent proteins (RFPs) is one of the “holy grails” of the protein engineering community. Despite several attempts, such fluorescent proteins (FPs) have remained elusive. One bottleneck to engineering next-generation RFPs is our lack of understanding of nonfluorescent or dark-state properties in such constructs. Here, we develop a theoretical and experimental framework that describes how photobleaching decays in FPs relate to dark-state conversion and ground-state recovery. Our systematic photophysical investigation of mCherry and mCherry-d, an RFP with enhanced dark-state behavior, showed the presence of photodestructive dark states in such FPs. Molecular dynamics simulations reveal enhanced fluctuation around the imidazolinone end of the chromophore in mCherry-d, potentially facilitating conversion to nonfluorescent states. Collectively, this work quantifies dark-state kinetics and provides insights into engineering dark states in RFPs to develop bright, yet photostable, molecular probes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462300","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 morphology and property of the high-temperature proton exchange membranes (PEMs) based on short-side-chain perfluorosulfonic acid (SSC-PFSA) are determined by the polymer structure in dispersion during solution casting. In this work, by using rheological analysis and structural characterization techniques, including Cryo-transmission electron microscope (Cryo-TEM) and small-angle X-ray scattering (SAXS), the rheology and microstructure of SSC-PFSA dispersions were collectively studied to spotlight the concentration dependent viscoelasticity across a large scale from dilute solution to gelation. Initially, SSC-PFSA forms rod-like primary aggregates exhibiting a scaling exponent (0.63) that deviates from the theoretical values of 0.5 (for semidilute solutions). As the concentration increases, these primary aggregates assemble into secondary aggregates, where the viscosity-concentration relationship deviates from the predicted scaling behavior. Further increasing the concentration, the secondary aggregates interact to form a percolating network, leading to gelation. This new multiscale self-assembly mechanism elucidates the fundamental connections underlying the gelation process toward membrane formation. It provides the first comprehensive understanding of the nonequilibrium morphology evolution across multiple magnitudes of concentration and length scales and finds the origin of the physical properties for SSC-PFSA electrolyte membranes.
{"title":"Viscoelasticity and Sol-Gel Transition via Multiscale Self-Assembled Nanostructures in Short-Side-Chain PFSA Dispersions.","authors":"Bonan Hao,Anyang Zhang,Jianpeng Jiang,Jingnan Song,Yanxin Zhao,Yecheng Zou,Zichun Zhou,Wei Yu,Feng Liu,Yongming Zhang","doi":"10.1021/acs.jpclett.6c00012","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00012","url":null,"abstract":"The morphology and property of the high-temperature proton exchange membranes (PEMs) based on short-side-chain perfluorosulfonic acid (SSC-PFSA) are determined by the polymer structure in dispersion during solution casting. In this work, by using rheological analysis and structural characterization techniques, including Cryo-transmission electron microscope (Cryo-TEM) and small-angle X-ray scattering (SAXS), the rheology and microstructure of SSC-PFSA dispersions were collectively studied to spotlight the concentration dependent viscoelasticity across a large scale from dilute solution to gelation. Initially, SSC-PFSA forms rod-like primary aggregates exhibiting a scaling exponent (0.63) that deviates from the theoretical values of 0.5 (for semidilute solutions). As the concentration increases, these primary aggregates assemble into secondary aggregates, where the viscosity-concentration relationship deviates from the predicted scaling behavior. Further increasing the concentration, the secondary aggregates interact to form a percolating network, leading to gelation. This new multiscale self-assembly mechanism elucidates the fundamental connections underlying the gelation process toward membrane formation. It provides the first comprehensive understanding of the nonequilibrium morphology evolution across multiple magnitudes of concentration and length scales and finds the origin of the physical properties for SSC-PFSA electrolyte membranes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461681","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 : 2026-03-16DOI: 10.1021/acs.jpclett.6c00350
Shiyan Gong,Peng Wang,Yuxiang Mo
We report the bond dissociation energy (BDE) of nitric oxide (NO) with subwavenumber precision (±0.20 cm–1), measured via state-to-state resolved threshold fragment yield spectroscopy. The ground-state dissociation limit, NO(X2Π1/2) → N(4S) + O(3P2), yields a BDE of 52396.92 ± 0.20 cm–1 (6.496390 ± 0.000025 eV; 626.8064 ± 0.0024 kJ/mol), reducing the uncertainty of prior work by a factor of 50. Combining this result with equally precise BDEs for N2, O2, CO, NO2, and CO2, we derive spectroscopically accurate thermochemical benchmarks, including ΔfH0(NO, 0 K), ΔfH0(NO2, 0 K), the atomization energy of NO2, the ion-pair dissociation energy of NO, the bond dissociation energies of NO+, and the reaction energies for seven key processes. The O(3P2) fragment angular distribution from NO(C2Π) predissociation provides direct experimental confirmation of spin–orbit interaction with the NO(a4Π) continuum. These results establish definitive benchmarks for thermochemistry and ab initio quantum chemistry, potentially advancing kinetic modeling in atmospheric chemistry, combustion, and NOx research.
{"title":"Bond Dissociation Energy of NO with Subwavenumber Precision via State-to-State Resolved Threshold Fragment Yield Spectroscopy","authors":"Shiyan Gong,Peng Wang,Yuxiang Mo","doi":"10.1021/acs.jpclett.6c00350","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00350","url":null,"abstract":"We report the bond dissociation energy (BDE) of nitric oxide (NO) with subwavenumber precision (±0.20 cm–1), measured via state-to-state resolved threshold fragment yield spectroscopy. The ground-state dissociation limit, NO(X2Π1/2) → N(4S) + O(3P2), yields a BDE of 52396.92 ± 0.20 cm–1 (6.496390 ± 0.000025 eV; 626.8064 ± 0.0024 kJ/mol), reducing the uncertainty of prior work by a factor of 50. Combining this result with equally precise BDEs for N2, O2, CO, NO2, and CO2, we derive spectroscopically accurate thermochemical benchmarks, including ΔfH0(NO, 0 K), ΔfH0(NO2, 0 K), the atomization energy of NO2, the ion-pair dissociation energy of NO, the bond dissociation energies of NO+, and the reaction energies for seven key processes. The O(3P2) fragment angular distribution from NO(C2Π) predissociation provides direct experimental confirmation of spin–orbit interaction with the NO(a4Π) continuum. These results establish definitive benchmarks for thermochemistry and ab initio quantum chemistry, potentially advancing kinetic modeling in atmospheric chemistry, combustion, and NOx research.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"130 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462266","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 : 2026-03-16DOI: 10.1021/acs.jpclett.5c03744
Yiqi Huo, Luo Yan, Shuo Li, Liujiang Zhou
Altermagnetism (AM), an unconventional spin-ordered phase, presents a unique platform for exploring ultrafast spin manipulation. However, the mechanisms underlying laser-driven spin dynamics in low-dimensional altermagnets remain largely unclear. Using real-time time-dependent density functional theory, we investigate laser-induced spin dynamics in d-wave AM V2Se2O-based crystals. Our results show that momentum-dependent spin transfer in them can be selectively excited by laser polarization, generating a transient net magnetization via anisotropic optical intersite spin transfer. Compared with K-intercalated bulk KV2Se2O, deintercalated bulk and monolayer V2Se2O exhibit a much larger laser-induced net magnetization, which is attributed to the K-intercalation controlled electronic reconstruction and the consequent suppression of spin-relaxation channels. These results establish dimensionality and K-intercalation as practical knobs to tailor ultrafast spin responses, highlighting altermagnets as viable candidates for ultrafast spintronic applications.
{"title":"Ultrafast Laser-Driven Asymmetric Demagnetization Dynamics in d-Wave Altermagnets","authors":"Yiqi Huo, Luo Yan, Shuo Li, Liujiang Zhou","doi":"10.1021/acs.jpclett.5c03744","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03744","url":null,"abstract":"Altermagnetism (AM), an unconventional spin-ordered phase, presents a unique platform for exploring ultrafast spin manipulation. However, the mechanisms underlying laser-driven spin dynamics in low-dimensional altermagnets remain largely unclear. Using real-time time-dependent density functional theory, we investigate laser-induced spin dynamics in <i>d</i>-wave AM V<sub>2</sub>Se<sub>2</sub>O-based crystals. Our results show that momentum-dependent spin transfer in them can be selectively excited by laser polarization, generating a transient net magnetization via anisotropic optical intersite spin transfer. Compared with K-intercalated bulk KV<sub>2</sub>Se<sub>2</sub>O, deintercalated bulk and monolayer V<sub>2</sub>Se<sub>2</sub>O exhibit a much larger laser-induced net magnetization, which is attributed to the K-intercalation controlled electronic reconstruction and the consequent suppression of spin-relaxation channels. These results establish dimensionality and K-intercalation as practical knobs to tailor ultrafast spin responses, highlighting altermagnets as viable candidates for ultrafast spintronic applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"91 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461847","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 : 2026-03-16DOI: 10.1021/acs.jpclett.6c00304
Yuting Sun,Qingyuan Zhao,Xiaoying Yu,Aijun Li,Hitoshi Tamiaki,Shin-ichi Sasaki,Yanhui Wang,Xiao-Feng Wang
Conventional photodetectors are typically limited to monochromatic image sensing, which is increasingly inadequate for modern applications. In this work, we demonstrate full-color image sensing using an organic photodetector (OPD) based on a ternary heterojunction comprising 131-deoxo-131-dicyanomethylene-pyropheophorbide-a (Chl), poly(3-hexylthiophene-2,5-diyl) (P3HT), and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM). Compared with the PC61BM:P3HT device, incorporating Chl effectively enhances the external quantum efficiency. This is mainly attributed to the lowest unoccupied molecular orbital and highest occupied molecular orbital energy levels of Chl lying between those of PC61BM and P3HT, which facilitates efficient extraction of electrons and holes. Moreover, by leveraging the device’s distinct responses at 475, 530, and 730 nm, color image sensing is realized in the self-powered mode, with the reconstructed images achieving a structural similarity index of up to 97% based on external RGB reconstruction. This study offers a new strategy for developing flexible and high-performance color imaging devices.
{"title":"Chlorophyll Derivative Enables High-Performance Self-Powered Organic Photodetectors for Full-Color Imaging","authors":"Yuting Sun,Qingyuan Zhao,Xiaoying Yu,Aijun Li,Hitoshi Tamiaki,Shin-ichi Sasaki,Yanhui Wang,Xiao-Feng Wang","doi":"10.1021/acs.jpclett.6c00304","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00304","url":null,"abstract":"Conventional photodetectors are typically limited to monochromatic image sensing, which is increasingly inadequate for modern applications. In this work, we demonstrate full-color image sensing using an organic photodetector (OPD) based on a ternary heterojunction comprising 131-deoxo-131-dicyanomethylene-pyropheophorbide-a (Chl), poly(3-hexylthiophene-2,5-diyl) (P3HT), and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM). Compared with the PC61BM:P3HT device, incorporating Chl effectively enhances the external quantum efficiency. This is mainly attributed to the lowest unoccupied molecular orbital and highest occupied molecular orbital energy levels of Chl lying between those of PC61BM and P3HT, which facilitates efficient extraction of electrons and holes. Moreover, by leveraging the device’s distinct responses at 475, 530, and 730 nm, color image sensing is realized in the self-powered mode, with the reconstructed images achieving a structural similarity index of up to 97% based on external RGB reconstruction. This study offers a new strategy for developing flexible and high-performance color imaging devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"233 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462263","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 : 2026-03-16DOI: 10.1021/acs.jpclett.6c00136
Yiheng Shen,Chang Liu,Wei Xie,Wei Ren
Hafnia (HfO2) is a silicon-compatible dielectric material, yet stabilizing its desired but metastable ferroelectric phase remains challenging. Phase stability predictions by density functional theory (DFT) have provided crucial guidance, but most simulations neglected or only treated finite temperature effects with (quasi)harmonic approximation due to the high computational cost of DFT. Here, we develop a machine learning force field and perform thermodynamic calculations for HfO2 using self-consistent phonon theory to address growing evidence of anharmonicity. Our results reveal that the ferroelectric orthorhombic phase oIII exhibits metastability below 0.1kBT under most conditions within the simulated regime of temperature and pressure (600 ≤ T ≤ 1500 K and 0 ≤ p ≤ 7.5 GPa), contradicting previous harmonic predictions of metastability above 1500 K at ambient pressure. We further report evidence for the temperature- and pressure-dependent ferroelectric parent phase despite efforts to identify a universal one. This study highlights the importance of anharmonicity and provides an effective approach to its treatment in the design of HfO2-based ferroelectrics.
{"title":"Anharmonic Thermodynamics Redefines Metastability and Parent Phases in Ferroelectric HfO2","authors":"Yiheng Shen,Chang Liu,Wei Xie,Wei Ren","doi":"10.1021/acs.jpclett.6c00136","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00136","url":null,"abstract":"Hafnia (HfO2) is a silicon-compatible dielectric material, yet stabilizing its desired but metastable ferroelectric phase remains challenging. Phase stability predictions by density functional theory (DFT) have provided crucial guidance, but most simulations neglected or only treated finite temperature effects with (quasi)harmonic approximation due to the high computational cost of DFT. Here, we develop a machine learning force field and perform thermodynamic calculations for HfO2 using self-consistent phonon theory to address growing evidence of anharmonicity. Our results reveal that the ferroelectric orthorhombic phase oIII exhibits metastability below 0.1kBT under most conditions within the simulated regime of temperature and pressure (600 ≤ T ≤ 1500 K and 0 ≤ p ≤ 7.5 GPa), contradicting previous harmonic predictions of metastability above 1500 K at ambient pressure. We further report evidence for the temperature- and pressure-dependent ferroelectric parent phase despite efforts to identify a universal one. This study highlights the importance of anharmonicity and provides an effective approach to its treatment in the design of HfO2-based ferroelectrics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"3 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147462264","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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