Pub Date : 2026-03-11DOI: 10.1021/acs.jpclett.5c03880
Junjie Guo,Mingke Li,Yulong Li,Wenle Tan,Lai Jiang,Bohan Wang,Lei Ying,Yue Yu,Yuguang Ma
Excitons in organic semiconductors exhibit an energy distribution due to molecular thermal motion and disordered molecular packing. In our previous work, we modeled the exciton energy distribution using a simple Gaussian function centered at the optical bandgap. By comparing the overlap area (Aex) between the model and the solution absorption spectra of the emitters, we demonstrated that emitters with a high density of band-tail states are conducive to achieving high device efficiency. Herein, we develop two new blue emitters, TCPN and NCPN, featuring hybridized local and charge transfer (HLCT) and localized excited (LE) states, respectively. We optimize the initial model, including replacing the solution absorption spectra with thin-film excitation spectra, keeping the total number of excitons constant while varying the degree of exciton dispersion, and using the overlap integral (Jex) instead of Aex. This work provides novel insights into designing high-efficiency emitters through the lens of the exciton energy distribution.
{"title":"High-Performance Nondoped Blue OLEDs Enabled by HLCT-State Emitters with High Excited Band-Tail Density: An Exciton Energy Distribution Perspective.","authors":"Junjie Guo,Mingke Li,Yulong Li,Wenle Tan,Lai Jiang,Bohan Wang,Lei Ying,Yue Yu,Yuguang Ma","doi":"10.1021/acs.jpclett.5c03880","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03880","url":null,"abstract":"Excitons in organic semiconductors exhibit an energy distribution due to molecular thermal motion and disordered molecular packing. In our previous work, we modeled the exciton energy distribution using a simple Gaussian function centered at the optical bandgap. By comparing the overlap area (Aex) between the model and the solution absorption spectra of the emitters, we demonstrated that emitters with a high density of band-tail states are conducive to achieving high device efficiency. Herein, we develop two new blue emitters, TCPN and NCPN, featuring hybridized local and charge transfer (HLCT) and localized excited (LE) states, respectively. We optimize the initial model, including replacing the solution absorption spectra with thin-film excitation spectra, keeping the total number of excitons constant while varying the degree of exciton dispersion, and using the overlap integral (Jex) instead of Aex. This work provides novel insights into designing high-efficiency emitters through the lens of the exciton energy distribution.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"54 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147393762","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 : 2026-03-11DOI: 10.1021/acs.jpclett.6c00179
Jhong-Ren Huang,Yi-Hsin Liu,Satoshi Kameoka,Lu-Sheng Hong
Metastable states near deep eutectic points are typically regarded as transient intermediates preceding phase separation, yet their potential chemical reactivity remains largely unexplored. Here, we demonstrate that metastable Au–Si bonding configurations derived from Au4Si near its deep eutectic temperature exhibit molecule-like reactivity associated with an sp3-like local bonding environment, enabling direct Si–C bond formation at temperatures as low as 636 K. Using a high-vacuum coevaporation platform, Au–Si species generated during coevaporation react with carbon clusters to produce SiC accompanied by Au segregation, whereas elemental Si under identical conditions remains chemically inert. Raman spectroscopy and X-ray photoelectron spectroscopy reveal that SiC formation occurs only within a narrow temperature window centered at the eutectic point and displays nonmonotonic temperature dependence inconsistent with conventional catalytic or vapor–liquid–solid mechanisms. These results provide experimental evidence that eutectic metastable bonding configurations can transiently adopt molecule-like characteristics, thereby enabling unconventional low-temperature reaction pathways in metal–semiconductor systems.
{"title":"Molecular sp3-like Reactivity of Metastable Au4Si near Its Deep Eutectic Point Enables Low-Temperature SiC Formation","authors":"Jhong-Ren Huang,Yi-Hsin Liu,Satoshi Kameoka,Lu-Sheng Hong","doi":"10.1021/acs.jpclett.6c00179","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00179","url":null,"abstract":"Metastable states near deep eutectic points are typically regarded as transient intermediates preceding phase separation, yet their potential chemical reactivity remains largely unexplored. Here, we demonstrate that metastable Au–Si bonding configurations derived from Au4Si near its deep eutectic temperature exhibit molecule-like reactivity associated with an sp3-like local bonding environment, enabling direct Si–C bond formation at temperatures as low as 636 K. Using a high-vacuum coevaporation platform, Au–Si species generated during coevaporation react with carbon clusters to produce SiC accompanied by Au segregation, whereas elemental Si under identical conditions remains chemically inert. Raman spectroscopy and X-ray photoelectron spectroscopy reveal that SiC formation occurs only within a narrow temperature window centered at the eutectic point and displays nonmonotonic temperature dependence inconsistent with conventional catalytic or vapor–liquid–solid mechanisms. These results provide experimental evidence that eutectic metastable bonding configurations can transiently adopt molecule-like characteristics, thereby enabling unconventional low-temperature reaction pathways in metal–semiconductor systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"124 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383820","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 : 2026-03-10DOI: 10.1021/acs.jpclett.6c00252
Mingtian Tang,Ying Wang,Nanqiu Zhang,Zhenghan Kan,Yongtao Zou,Yanwei Huang,Xiaozhi Yan
Conventional high-temperature sintering of oxide solid electrolytes often induces lithium loss, impurity formation, and microstructural defects, which severely compromise the ionic conductivity. To overcome these limitations, a high-pressure, low-temperature (HP-LT) sintering strategy is developed. This process produces a highly dense (94.2%) NASICON-type Li1+xAlxTi2-x(PO4)3 (LATP) ceramic at low temperatures, exhibiting a remarkable room-temperature ionic conductivity of 9.46 × 10-4 S/cm, 4 times that of conventionally sintered counterparts. Comprehensive characterizations, including XRD, SEM, density, and electrochemical impedance measurements, reveal that the enhanced performance originates from the effective suppression of material decomposition and the significant promotion of interfacial ionic transport enabled by the HP-LT approach. This work demonstrates HP-LT synthesis as an efficient and scalable route for fabricating high-performance LATP electrolytes, paving the way toward advanced all-solid-state batteries.
{"title":"High-Pressure, Low-Temperature Synthesis of Li1+xAlxTi2-x(PO4)3 Solid Electrolytes for High-Performance Solid-State Batteries.","authors":"Mingtian Tang,Ying Wang,Nanqiu Zhang,Zhenghan Kan,Yongtao Zou,Yanwei Huang,Xiaozhi Yan","doi":"10.1021/acs.jpclett.6c00252","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00252","url":null,"abstract":"Conventional high-temperature sintering of oxide solid electrolytes often induces lithium loss, impurity formation, and microstructural defects, which severely compromise the ionic conductivity. To overcome these limitations, a high-pressure, low-temperature (HP-LT) sintering strategy is developed. This process produces a highly dense (94.2%) NASICON-type Li1+xAlxTi2-x(PO4)3 (LATP) ceramic at low temperatures, exhibiting a remarkable room-temperature ionic conductivity of 9.46 × 10-4 S/cm, 4 times that of conventionally sintered counterparts. Comprehensive characterizations, including XRD, SEM, density, and electrochemical impedance measurements, reveal that the enhanced performance originates from the effective suppression of material decomposition and the significant promotion of interfacial ionic transport enabled by the HP-LT approach. This work demonstrates HP-LT synthesis as an efficient and scalable route for fabricating high-performance LATP electrolytes, paving the way toward advanced all-solid-state batteries.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"77 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381369","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 : 2026-03-10DOI: 10.1021/acs.jpclett.6c00162
Chuan Cheng,Yoshiaki Kumagai,Kiyonobu Nagaya,Tatsuo Gejo,James Harries,Michael Burt,Mark Brouard,Avijit Duley,Paul Hockett,Joseph W McManus,Russell S Minns,Subhendu Mondal,Shigeki Owada,Weronika Razmus,Daniel Rolles,Takahiro Sato,Henry J Thompson,Anbu S Venkatachalam,Emily M Warne,Tiffany Walmsley,Mana Yagi,Philip Bucksbaum,Felix Allum,Ruaridh Forbes
Coulomb explosion imaging (CEI) provides a direct means of imaging molecular geometry by correlating fragment ion momenta following the fragmentation of a molecular polycation. Here, we demonstrate the use of three-body covariance and four-body cumulant analysis to extract three-dimensional (3D) structural information from the X-ray-induced Coulomb explosion of tert-butyl iodide (C4H9I). Site-selective ionization at the iodine 4d edge with intense femtosecond soft X-ray pulses from an X-ray free-electron laser (XFEL) enables rapid charge buildup and molecular breakup. By correlating ionic fragments in the molecular frame, we isolate complete dissociation channels and reveal subtle structural changes, such as umbrella-type motion of the branched alkyl chain, during the ionization process. Comparison with point-charge simulations of the Coulomb explosion shows close agreement, validating the approach. These results establish covariance/cumulant mapping as a powerful strategy for imaging complex three-dimensional molecular structures and point the way toward time-resolved CEI using both XFEL and tabletop sources for capturing ultrafast structural dynamics.
{"title":"Imaging Three-Dimensional Molecular Structure and Dynamics with Multiparticle Covariance and Cumulant Coulomb Explosion Analysis.","authors":"Chuan Cheng,Yoshiaki Kumagai,Kiyonobu Nagaya,Tatsuo Gejo,James Harries,Michael Burt,Mark Brouard,Avijit Duley,Paul Hockett,Joseph W McManus,Russell S Minns,Subhendu Mondal,Shigeki Owada,Weronika Razmus,Daniel Rolles,Takahiro Sato,Henry J Thompson,Anbu S Venkatachalam,Emily M Warne,Tiffany Walmsley,Mana Yagi,Philip Bucksbaum,Felix Allum,Ruaridh Forbes","doi":"10.1021/acs.jpclett.6c00162","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00162","url":null,"abstract":"Coulomb explosion imaging (CEI) provides a direct means of imaging molecular geometry by correlating fragment ion momenta following the fragmentation of a molecular polycation. Here, we demonstrate the use of three-body covariance and four-body cumulant analysis to extract three-dimensional (3D) structural information from the X-ray-induced Coulomb explosion of tert-butyl iodide (C4H9I). Site-selective ionization at the iodine 4d edge with intense femtosecond soft X-ray pulses from an X-ray free-electron laser (XFEL) enables rapid charge buildup and molecular breakup. By correlating ionic fragments in the molecular frame, we isolate complete dissociation channels and reveal subtle structural changes, such as umbrella-type motion of the branched alkyl chain, during the ionization process. Comparison with point-charge simulations of the Coulomb explosion shows close agreement, validating the approach. These results establish covariance/cumulant mapping as a powerful strategy for imaging complex three-dimensional molecular structures and point the way toward time-resolved CEI using both XFEL and tabletop sources for capturing ultrafast structural dynamics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"7 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383696","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}
Scintillators for X-ray imaging have gained significant interest due to their essential roles in medical diagnostics, security screening, and industrial inspection. However, conventional scintillators often suffer from limitations, such as a low light output efficiency or poor stability. Herein, we report a novel bilayer scintillator based on copper halide nanocrystals, comprising Cs3Cu2Cl5/Cs3Cu2I5 nanocrystals, which exhibits better performance in X-ray imaging. By optimization of the copper halide nanocrystal passivated with ammonium halides, the photoluminescence quantum yield can be increased from 41.85 to 66.18%, facilitating the performance of these bilayer copper-based halide scintillators. It utilizes energy-dependent attenuation contrast generated through differential X-ray absorption in the bilayer copper-based halide scintillators to generate dual-energy X-ray imaging. Moreover, the all-inorganic composition ensures the exceptional stability of the scintillator under prolonged X-ray irradiation. This study presents an innovative approach for developing next-generation, high-performance, and cost-effective X-ray imaging scintillators.
{"title":"Dual-Energy X-ray Imaging Enabled by Passivated Bilayer Copper-Based Halide Scintillators.","authors":"Yaoming Zhu,Chengjun Liu,Yuwei Li,Junyu Li,Wei Lei,Xiaobao Xu,Jing Chen","doi":"10.1021/acs.jpclett.6c00536","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00536","url":null,"abstract":"Scintillators for X-ray imaging have gained significant interest due to their essential roles in medical diagnostics, security screening, and industrial inspection. However, conventional scintillators often suffer from limitations, such as a low light output efficiency or poor stability. Herein, we report a novel bilayer scintillator based on copper halide nanocrystals, comprising Cs3Cu2Cl5/Cs3Cu2I5 nanocrystals, which exhibits better performance in X-ray imaging. By optimization of the copper halide nanocrystal passivated with ammonium halides, the photoluminescence quantum yield can be increased from 41.85 to 66.18%, facilitating the performance of these bilayer copper-based halide scintillators. It utilizes energy-dependent attenuation contrast generated through differential X-ray absorption in the bilayer copper-based halide scintillators to generate dual-energy X-ray imaging. Moreover, the all-inorganic composition ensures the exceptional stability of the scintillator under prolonged X-ray irradiation. This study presents an innovative approach for developing next-generation, high-performance, and cost-effective X-ray imaging scintillators.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"14 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147383697","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 : 2026-03-10DOI: 10.1021/acs.jpclett.6c00047
Sei Tsukamura,Yoshifumi Nishimura,Hiromi Nakai
Fluctuation-assisted molecular dynamics (FMD) is developed as an enhanced sampling approach for efficiently exploring chemical reactions and generating reaction events within picosecond to subnanosecond time scales in quantum mechanical molecular dynamics (MD) simulations. In the FMD framework, the effective collision frequency among reactants is increased by restraining chemical species toward the center of fluctuation by using a harmonic potential with a time-dependent force constant, thereby promoting reactive encounters within a confined reaction space. The polymerization reactivity of a homogeneous acetylene system is investigated using FMD and compared with nanoreactor MD, a reaction discovery method based on high-temperature and high-pressure conditions induced by periodic compression and expansion of the simulation volume. Although both approaches exhibit comparable accelerations in reactant consumption and reaction event generation, the FMD method achieves this enhancement under significantly milder temperature and pressure conditions. These results demonstrate that FMD provides an efficient and physically moderate strategy for enhanced sampling of complex chemical reaction processes near equilibrium.
{"title":"Development of a Fluctuation-Assisted Molecular Dynamics Method for the Efficient Exploration of Chemical Reactions.","authors":"Sei Tsukamura,Yoshifumi Nishimura,Hiromi Nakai","doi":"10.1021/acs.jpclett.6c00047","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00047","url":null,"abstract":"Fluctuation-assisted molecular dynamics (FMD) is developed as an enhanced sampling approach for efficiently exploring chemical reactions and generating reaction events within picosecond to subnanosecond time scales in quantum mechanical molecular dynamics (MD) simulations. In the FMD framework, the effective collision frequency among reactants is increased by restraining chemical species toward the center of fluctuation by using a harmonic potential with a time-dependent force constant, thereby promoting reactive encounters within a confined reaction space. The polymerization reactivity of a homogeneous acetylene system is investigated using FMD and compared with nanoreactor MD, a reaction discovery method based on high-temperature and high-pressure conditions induced by periodic compression and expansion of the simulation volume. Although both approaches exhibit comparable accelerations in reactant consumption and reaction event generation, the FMD method achieves this enhancement under significantly milder temperature and pressure conditions. These results demonstrate that FMD provides an efficient and physically moderate strategy for enhanced sampling of complex chemical reaction processes near equilibrium.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381367","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 : 2026-03-10DOI: 10.1021/acs.jpclett.6c00400
Daniel J Heintzelman,Kenneth L Knappenberger
Sub-to-few-nanometer gold nanoclusters exhibit a manifold of electronic states that result in nanocluster- and state-specific mechanisms of energy flow, which present new opportunities for developing photonic materials. Due to the spectral congestion of conventional ultrafast transient methods, mechanistic insights into energy flow are difficult to achieve for these systems. The use of two-dimensional electronic spectroscopy (2DES) to resolve electronic relaxation dynamics with state specificity for metal nanoclusters is described, along with prospects for future research. Excitation-detection frequency correlations inherent to 2D measurements resolve the electronic relaxation within specific gold superatom states. The state specificity of 2DES is extended to distinguish the influences of the electronic state symmetry on carrier relaxation using polarization-dependent measurements. Crosspeak-specific 2DES has also been used to distinguish sequential relaxation through nondegenerate electronic state manifolds of nanoclusters from the collective dynamics of metallic nanoparticles. These results demonstrate the power of 2DES for aiding the understanding of metal nanocluster photophysical properties.
{"title":"Resolving State-Specific Energy Flow in Metal Nanoclusters Using 2D Electronic Spectroscopy.","authors":"Daniel J Heintzelman,Kenneth L Knappenberger","doi":"10.1021/acs.jpclett.6c00400","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00400","url":null,"abstract":"Sub-to-few-nanometer gold nanoclusters exhibit a manifold of electronic states that result in nanocluster- and state-specific mechanisms of energy flow, which present new opportunities for developing photonic materials. Due to the spectral congestion of conventional ultrafast transient methods, mechanistic insights into energy flow are difficult to achieve for these systems. The use of two-dimensional electronic spectroscopy (2DES) to resolve electronic relaxation dynamics with state specificity for metal nanoclusters is described, along with prospects for future research. Excitation-detection frequency correlations inherent to 2D measurements resolve the electronic relaxation within specific gold superatom states. The state specificity of 2DES is extended to distinguish the influences of the electronic state symmetry on carrier relaxation using polarization-dependent measurements. Crosspeak-specific 2DES has also been used to distinguish sequential relaxation through nondegenerate electronic state manifolds of nanoclusters from the collective dynamics of metallic nanoparticles. These results demonstrate the power of 2DES for aiding the understanding of metal nanocluster photophysical properties.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"55 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381365","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}
Extracting hot carriers prior to thermalization is a long-standing challenge for surpassing the Shockley-Queisser limit in photovoltaic and optoelectronic devices. Antimony selenide (Sb2Se3), featuring quasi-one-dimensional ribbon-like crystal motifs, has recently emerged as a promising platform for hot-carrier utilization. However, directly resolving the associated ultrafast extraction current remains elusive. Here, by employing polarization-phase-resolved THz emission spectroscopy, we visualized the directed transient hot-electron extraction current at the Sb2Se3/SnO2 interface and identify an ∼1.2 eV pump photon energy threshold by a Fowler-type photoemission model, consistent with the direct band gap of the Sb2Se3. These results position THz emission spectroscopy as a powerful, noncontact metrology for mapping ultrafast and anisotropic hot-carrier dynamics and provide design principles for directional hot-carrier management in Sb2Se3-based energy-conversion devices.
{"title":"Directed Hot-Electron Transport in Quasi-One-Dimensional Antimony Selenide.","authors":"Zeyu Zhang,Huidi Jiang,Xinzhi Zu,Chunwei Wang,Weiqi Chen,Xiuchen Nie,Zhengzheng Liu,Zhiping Hu,Chao Chen,Jiang Tang,Yuxin Leng,Juan Du","doi":"10.1021/acs.jpclett.6c00340","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00340","url":null,"abstract":"Extracting hot carriers prior to thermalization is a long-standing challenge for surpassing the Shockley-Queisser limit in photovoltaic and optoelectronic devices. Antimony selenide (Sb2Se3), featuring quasi-one-dimensional ribbon-like crystal motifs, has recently emerged as a promising platform for hot-carrier utilization. However, directly resolving the associated ultrafast extraction current remains elusive. Here, by employing polarization-phase-resolved THz emission spectroscopy, we visualized the directed transient hot-electron extraction current at the Sb2Se3/SnO2 interface and identify an ∼1.2 eV pump photon energy threshold by a Fowler-type photoemission model, consistent with the direct band gap of the Sb2Se3. These results position THz emission spectroscopy as a powerful, noncontact metrology for mapping ultrafast and anisotropic hot-carrier dynamics and provide design principles for directional hot-carrier management in Sb2Se3-based energy-conversion devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"28 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381366","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 : 2026-03-09DOI: 10.1021/acs.jpclett.5c04034
Charlotte Titeca, Yifan Jiang, Frank De Proft, Thomas-C. Jagau
The use of a complex absorbing potential (CAP) for the description of temporary anions is well established. However, its combination with Kohn–Sham density functional theory (DFT) has so far been limited to the local density approximation. We report an implementation of CAP-DFT and complex-variable density functional approximations up to the generalized gradient approximation and derived hybrid functionals, which enables fast and accurate evaluation of the energies and lifetimes of metastable molecular anions. This new method is applied to various molecular systems, including the metastable anions of molecular nitrogen, formaldehyde, formic acid, ethene, and pyrene. Our results indicate that pure density functional approximations place temporary anions too low in energy and overestimate their decay width, while Hartree–Fock theory shows the opposite trends. Hybrid functionals balance these trends and deliver results that are competitive with equation-of-motion coupled-cluster theory.
{"title":"Density Functional Theory with Complex Absorbing Potentials: A Fast and Accurate Way of Modeling Metastable Anions","authors":"Charlotte Titeca, Yifan Jiang, Frank De Proft, Thomas-C. Jagau","doi":"10.1021/acs.jpclett.5c04034","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04034","url":null,"abstract":"The use of a complex absorbing potential (CAP) for the description of temporary anions is well established. However, its combination with Kohn–Sham density functional theory (DFT) has so far been limited to the local density approximation. We report an implementation of CAP-DFT and complex-variable density functional approximations up to the generalized gradient approximation and derived hybrid functionals, which enables fast and accurate evaluation of the energies and lifetimes of metastable molecular anions. This new method is applied to various molecular systems, including the metastable anions of molecular nitrogen, formaldehyde, formic acid, ethene, and pyrene. Our results indicate that pure density functional approximations place temporary anions too low in energy and overestimate their decay width, while Hartree–Fock theory shows the opposite trends. Hybrid functionals balance these trends and deliver results that are competitive with equation-of-motion coupled-cluster theory.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381080","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}
Ultrafast excitation energy transfer (EET) is studied for a supramolecular rhodamine-BODIPY dyad, which exemplifies EET systems that fall into a non-Förster regime where coherent effects are important. A key question that arises concerns the transition between coherent and kinetic transfer regimes, which is addressed here based on real-time quantum dynamics and the time-evolving state-to-state flux that transitions from early time transients to a quasi-stationary regime. Multiconfigurational wavepacket calculations are carried out using the two-layer Gaussian-based multiconfiguration time-dependent Hartree (2L-GMCTDH) method, in conjunction with the thermofield dynamics method in order to include thermalization of low-frequency modes. Several characteristic time scales are identified that are intimately connected to the flux evolution and decoherence phenomena. An almost fully decoherent state is reached at around 75 fs, but the purity is restored to a large extent as the transfer to the acceptor state proceeds. It is found that the ultrafast EET step that is almost complete at around 200 fs is mediated by vibronic resonance effects, which lead to an athermal nonequilibrium state of the donor moiety, exhibiting mode-selective vibrational excitation following the EET transfer. A slower time scale associated with a kinetic regime shows a non-negligible temperature dependence.
{"title":"Excitation Energy Transfer in an Intermediate Regime: A Multiconfigurational Gaussian Wavepacket Study of a Light-Harvesting Supramolecular Dyad","authors":"Sreeja Loho Choudhury, Maximiliane Horz, Rainer Hegger, Rocco Martinazzo, Irene Burghardt","doi":"10.1021/acs.jpclett.6c00100","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00100","url":null,"abstract":"Ultrafast excitation energy transfer (EET) is studied for a supramolecular rhodamine-BODIPY dyad, which exemplifies EET systems that fall into a non-Förster regime where coherent effects are important. A key question that arises concerns the transition between coherent and kinetic transfer regimes, which is addressed here based on real-time quantum dynamics and the time-evolving state-to-state flux that transitions from early time transients to a quasi-stationary regime. Multiconfigurational wavepacket calculations are carried out using the two-layer Gaussian-based multiconfiguration time-dependent Hartree (2L-GMCTDH) method, in conjunction with the thermofield dynamics method in order to include thermalization of low-frequency modes. Several characteristic time scales are identified that are intimately connected to the flux evolution and decoherence phenomena. An almost fully decoherent state is reached at around 75 fs, but the purity is restored to a large extent as the transfer to the acceptor state proceeds. It is found that the ultrafast EET step that is almost complete at around 200 fs is mediated by vibronic resonance effects, which lead to an athermal nonequilibrium state of the donor moiety, exhibiting mode-selective vibrational excitation following the EET transfer. A slower time scale associated with a kinetic regime shows a non-negligible temperature dependence.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"127 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381082","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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