Pub Date : 2025-12-13DOI: 10.1021/acs.jpclett.5c03411
Marc de Wergifosse
Computing a near-edge X-ray absorption fine structure (NEXAFS) is a real challenge for quantum chemistry (QC), as for medium to large systems, it involves a high density of core-valence excited states. With the boundaries of QC pushed at its maximum with the exact integral simplified time-dependent density functional theory (XsTD-DFT) framework, an ultrafast method is proposed to compute such excitations with short-range corrected exchange-correlation functionals using the Tamm-Dancoff approximation. For small to medium size systems, computations were performed in less than a minute, providing striking comparisons with respect to the experiment. To showcase the performance of the method, the computed oxygen K-edge NEXAFS spectrum for a collagen model of 600 atoms was compared to the experimental spectrum of collagen. Computing 85 672 1sO core-valence excited states was necessary to reproduce the experimental spectrum. The calculation took only 11 days on a desktop computer. With knowledge of the simplicity of this "small" static model of collagen, the comparison to the experiment remains excellent.
{"title":"Ultrafast Near-Edge X-ray Absorption Fine Structure Calculations with the Exact Integral Simplified Time-Dependent Density Functional Theory (XsTD-DFT) for Large Systems.","authors":"Marc de Wergifosse","doi":"10.1021/acs.jpclett.5c03411","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03411","url":null,"abstract":"Computing a near-edge X-ray absorption fine structure (NEXAFS) is a real challenge for quantum chemistry (QC), as for medium to large systems, it involves a high density of core-valence excited states. With the boundaries of QC pushed at its maximum with the exact integral simplified time-dependent density functional theory (XsTD-DFT) framework, an ultrafast method is proposed to compute such excitations with short-range corrected exchange-correlation functionals using the Tamm-Dancoff approximation. For small to medium size systems, computations were performed in less than a minute, providing striking comparisons with respect to the experiment. To showcase the performance of the method, the computed oxygen K-edge NEXAFS spectrum for a collagen model of 600 atoms was compared to the experimental spectrum of collagen. Computing 85 672 1sO core-valence excited states was necessary to reproduce the experimental spectrum. The calculation took only 11 days on a desktop computer. With knowledge of the simplicity of this \"small\" static model of collagen, the comparison to the experiment remains excellent.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"157 1","pages":"13132-13138"},"PeriodicalIF":6.475,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732829","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 : 2025-12-13DOI: 10.1021/acs.jpclett.5c03349
Guiying He, Sihan Chen, Rongchao Jin
Atomically precise metal nanoclusters (NCs) have attracted wide research interest. In terms of electronic properties, a striking feature of such NCs is triplet excited state generation with remarkably high efficiency. Experimental and theoretical findings indicate that NCs are promising luminescent materials with room-temperature phosphorescence and thermally activated delayed fluorescence. However, the manipulation of triplet formation remains difficult due to the complexity of the electron dynamics in NCs. In this Perspective, we summarize recent advances in fundamental research on this topic. We first illustrate the typical spectral features of the triplet state and analytical methods such as time-resolved photoluminescence (TR-PL), transient absorption (TA), and temperature-dependent PL spectroscopies. We then focus on the recent understating of triplet states in NCs and how to manipulate the triplet states. Finally, we present the remaining challenges and future outlooks. This Perspective aims to contribute to the further design of NCs for efficient ISC processes and applications of the triplet states. With a fundamental understanding of the triplet states in NCs, one may develop star materials for triplet utilization in optoelectronics, photocatalysis, and near-infrared solar energy upconversion.
{"title":"Manipulating the Intersystem Crossing Process in Atomically Precise Gold Nanoclusters","authors":"Guiying He, Sihan Chen, Rongchao Jin","doi":"10.1021/acs.jpclett.5c03349","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03349","url":null,"abstract":"Atomically precise metal nanoclusters (NCs) have attracted wide research interest. In terms of electronic properties, a striking feature of such NCs is triplet excited state generation with remarkably high efficiency. Experimental and theoretical findings indicate that NCs are promising luminescent materials with room-temperature phosphorescence and thermally activated delayed fluorescence. However, the manipulation of triplet formation remains difficult due to the complexity of the electron dynamics in NCs. In this Perspective, we summarize recent advances in fundamental research on this topic. We first illustrate the typical spectral features of the triplet state and analytical methods such as time-resolved photoluminescence (TR-PL), transient absorption (TA), and temperature-dependent PL spectroscopies. We then focus on the recent understating of triplet states in NCs and how to manipulate the triplet states. Finally, we present the remaining challenges and future outlooks. This Perspective aims to contribute to the further design of NCs for efficient ISC processes and applications of the triplet states. With a fundamental understanding of the triplet states in NCs, one may develop star materials for triplet utilization in optoelectronics, photocatalysis, and near-infrared solar energy upconversion.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"56 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731825","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c03120
N. Mauger, A. Benali, K. D. Jordan
Coupled cluster singles and doubles with perturbative triples [CCSD(T)] and single determinant fixed-node diffusion Monte Carlo (SD-DMC) have emerged as two of the most useful methods for providing benchmark reaction and interaction energies of chemical systems without strong static correlation. The errors in DMC energies are dominated by an inexact description of the nodal surfaces for electron exchange. One of the main approaches to addressing the fixed-node error is to use multideterminant (MD) trial wave functions. We consider here the energy differences between pairs of related molecules with aromatic and quinoidal structures as well as between quinoidal isomers. Quinoidal systems tend to have some diradical character, leading one to anticipate that SD-DMC calculations may face challenges in accurately describing their energetics. The MD trial wave functions were generated from the complete active space calculations. A comparison is made with the predictions of well-converged CCSD(T) calculations.
{"title":"Performance of Diffusion Monte Carlo Calculations for Predicting the Relative Energies of Quinoidal and Nonquinoidal Species","authors":"N. Mauger, A. Benali, K. D. Jordan","doi":"10.1021/acs.jpclett.5c03120","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03120","url":null,"abstract":"Coupled cluster singles and doubles with perturbative triples [CCSD(T)] and single determinant fixed-node diffusion Monte Carlo (SD-DMC) have emerged as two of the most useful methods for providing benchmark reaction and interaction energies of chemical systems without strong static correlation. The errors in DMC energies are dominated by an inexact description of the nodal surfaces for electron exchange. One of the main approaches to addressing the fixed-node error is to use multideterminant (MD) trial wave functions. We consider here the energy differences between pairs of related molecules with aromatic and quinoidal structures as well as between quinoidal isomers. Quinoidal systems tend to have some diradical character, leading one to anticipate that SD-DMC calculations may face challenges in accurately describing their energetics. The MD trial wave functions were generated from the complete active space calculations. A comparison is made with the predictions of well-converged CCSD(T) calculations.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"42 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731822","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c03144
Logan E. Smith, Valentín Briega-Martos, Yao Yang, Sharon Hammes-Schiffer
Hydrogen/deuterium (H/D) substitution at electrochemical interfaces can provide insights into fundamental electrochemical processes. Periodic nuclear–electronic orbital density functional theory (NEO-DFT), which treats specified nuclei quantum mechanically on the same level as the electrons, enables such H/D isotope effects to be investigated computationally. Herein, periodic NEO-DFT is applied to OH–/OD– adsorption, H/D adsorption, and H2O/D2O monolayers at a Pt(111) surface. These calculations inherently include anharmonic zero-point energy and nuclear delocalization of hydrogen and deuterium. Thus, they capture structural differences between H/D isotopologues, guide interpretation of experimental cyclic voltammograms, identify favored adsorption sites, and characterize differences in H2O/D2O hydrogen-bonding interactions. Periodic NEO-DFT maintains the favorable computational scaling of conventional DFT, predicts geometric isotope effects, and can be combined with techniques to model an applied potential. Thus, periodic NEO-DFT represents a promising tool for probing the structures of electrochemical interfaces, interpreting experimental isotope studies, and elucidating electrocatalytic mechanisms.
{"title":"Isotope Effects for Water at Pt(111) Computed with Nuclear−Electronic Orbital Theory","authors":"Logan E. Smith, Valentín Briega-Martos, Yao Yang, Sharon Hammes-Schiffer","doi":"10.1021/acs.jpclett.5c03144","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03144","url":null,"abstract":"Hydrogen/deuterium (H/D) substitution at electrochemical interfaces can provide insights into fundamental electrochemical processes. Periodic nuclear–electronic orbital density functional theory (NEO-DFT), which treats specified nuclei quantum mechanically on the same level as the electrons, enables such H/D isotope effects to be investigated computationally. Herein, periodic NEO-DFT is applied to OH<sup>–</sup>/OD<sup>–</sup> adsorption, H/D adsorption, and H<sub>2</sub>O/D<sub>2</sub>O monolayers at a Pt(111) surface. These calculations inherently include anharmonic zero-point energy and nuclear delocalization of hydrogen and deuterium. Thus, they capture structural differences between H/D isotopologues, guide interpretation of experimental cyclic voltammograms, identify favored adsorption sites, and characterize differences in H<sub>2</sub>O/D<sub>2</sub>O hydrogen-bonding interactions. Periodic NEO-DFT maintains the favorable computational scaling of conventional DFT, predicts geometric isotope effects, and can be combined with techniques to model an applied potential. Thus, periodic NEO-DFT represents a promising tool for probing the structures of electrochemical interfaces, interpreting experimental isotope studies, and elucidating electrocatalytic mechanisms.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729091","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}
Cell-penetrating peptides (CPPs) exhibit concentration-dependent efficiency limitations in transmembrane delivery; however, elucidating the molecular mechanism of this concentration dependence from the perspective of interface interaction with phospholipid membranes remains unclear. Here, we employed in situ high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS/SFG-VS) to probe molecular-level interactions between penetrating peptide (PEN) and egg sphingomyelin (ESM) monolayers at the air-water interface. Our study reveals three interconnected mechanisms to govern PEN-ESM interfacial evolution related to this concentration dependence. PEN insertion exhibits a nonmonotonic concentration threshold effect that balances structural ordering promotion and disruption while dictating efficiency transitions. Simultaneously, asymmetric chain reorganization occurs with sphingosine terminal methyl orientation shifts modulated by lipid packing density and PEN concentration, showing angular variations from 32° to 55°, whereas N-alkyl chain terminal methyl angles remain stable between 32° and 38°. Furthermore, the lipid packing density and PEN concentration synergistically regulate interfacial hydrogen-bond networks and adsorption states. At high lipid density such as 30 mN/m, elevated hydrogen-bond network proportions correlate with non-hydrogen-bonded PEN carbonyl states. Conversely, low density conditions such as 10 mN/m reduce network proportions and promote hydrogen-bonded adsorption. Crucially, efficient CPP translocation requires balancing amphipathic domain interactions with dynamic bilayer restructuring, with nonlinear ordering transitions identifying critical thresholds for transmembrane insertion. Lipid packing density and PEN concentration jointly orchestrate interfacial perturbation modes, demonstrating their pivotal role in governing molecular transport efficiency. Our work also demonstrates the unique capability of SFG-VS for resolving such interfacial dynamics, which can offer fundamental insights for designing functional membrane systems.
{"title":"In Situ Probing the Effects of Lipid Packing Density and Concentration of CPPs on the Transmembrane Process at the Air-Water Interface.","authors":"Linyu Han,Caihe Liu,Yuening Zhang,Xujin Qin,Yuan Guo,Minghua Liu,Zhen Zhang","doi":"10.1021/acs.jpclett.5c02798","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02798","url":null,"abstract":"Cell-penetrating peptides (CPPs) exhibit concentration-dependent efficiency limitations in transmembrane delivery; however, elucidating the molecular mechanism of this concentration dependence from the perspective of interface interaction with phospholipid membranes remains unclear. Here, we employed in situ high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS/SFG-VS) to probe molecular-level interactions between penetrating peptide (PEN) and egg sphingomyelin (ESM) monolayers at the air-water interface. Our study reveals three interconnected mechanisms to govern PEN-ESM interfacial evolution related to this concentration dependence. PEN insertion exhibits a nonmonotonic concentration threshold effect that balances structural ordering promotion and disruption while dictating efficiency transitions. Simultaneously, asymmetric chain reorganization occurs with sphingosine terminal methyl orientation shifts modulated by lipid packing density and PEN concentration, showing angular variations from 32° to 55°, whereas N-alkyl chain terminal methyl angles remain stable between 32° and 38°. Furthermore, the lipid packing density and PEN concentration synergistically regulate interfacial hydrogen-bond networks and adsorption states. At high lipid density such as 30 mN/m, elevated hydrogen-bond network proportions correlate with non-hydrogen-bonded PEN carbonyl states. Conversely, low density conditions such as 10 mN/m reduce network proportions and promote hydrogen-bonded adsorption. Crucially, efficient CPP translocation requires balancing amphipathic domain interactions with dynamic bilayer restructuring, with nonlinear ordering transitions identifying critical thresholds for transmembrane insertion. Lipid packing density and PEN concentration jointly orchestrate interfacial perturbation modes, demonstrating their pivotal role in governing molecular transport efficiency. Our work also demonstrates the unique capability of SFG-VS for resolving such interfacial dynamics, which can offer fundamental insights for designing functional membrane systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"37 1","pages":"13027-13037"},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728632","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c03652
Emir S. Amirov, Dongyu Liu, Mikhail R. Samatov, Dmitrii A. Abrameshin, Andrey E. Abrameshin, Alexander S. Kramarenko, Pavel A. Troshin, Weibin Chu, Huanping Zhou, Andrey S. Vasenko, Oleg V. Prezhdo
Cs2AgBiBr6 is a promising lead-free double perovskite with excellent stability, but it suffers from a large bandgap for optoelectronic applications. Hydrogenation is reported not only to reduce the bandgap but also to prolong the carrier lifetime in Cs2AgBiBr6, improving device efficiencies significantly. In order to elucidate the mechanisms underlying these phenomena, we combine density functional theory and nonadiabatic molecular dynamics and reveal the role of hydrogen (H) atoms in Cs2AgBiBr6. We demonstrate that H atoms spontaneously undergo a disproportionation reaction to form H+ and H–. The H– anions form chemical bonds with the Bi3+ cations and introduce midgap states to reduce the bandgap, with the calculated bandgap change comparable to the experimental observation. Moreover, these states facilitate electron–hole separation in Cs2AgBiBr6, suppressing their recombination and, thus, extending the carrier lifetime, despite the reduced bandgap. Our results rationalize the experimental phenomena and provide crucial insights into the development of novel lead-free perovskite materials.
{"title":"Hydrogen Disproportionation Reduces the Bandgap and Prolongs the Carrier Lifetime in Cs2AgBiBr6: Quantum Dynamics Analysis","authors":"Emir S. Amirov, Dongyu Liu, Mikhail R. Samatov, Dmitrii A. Abrameshin, Andrey E. Abrameshin, Alexander S. Kramarenko, Pavel A. Troshin, Weibin Chu, Huanping Zhou, Andrey S. Vasenko, Oleg V. Prezhdo","doi":"10.1021/acs.jpclett.5c03652","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03652","url":null,"abstract":"Cs<sub>2</sub>AgBiBr<sub>6</sub> is a promising lead-free double perovskite with excellent stability, but it suffers from a large bandgap for optoelectronic applications. Hydrogenation is reported not only to reduce the bandgap but also to prolong the carrier lifetime in Cs<sub>2</sub>AgBiBr<sub>6</sub>, improving device efficiencies significantly. In order to elucidate the mechanisms underlying these phenomena, we combine density functional theory and nonadiabatic molecular dynamics and reveal the role of hydrogen (H) atoms in Cs<sub>2</sub>AgBiBr<sub>6</sub>. We demonstrate that H atoms spontaneously undergo a disproportionation reaction to form H<sup>+</sup> and H<sup>–</sup>. The H<sup>–</sup> anions form chemical bonds with the Bi<sup>3+</sup> cations and introduce midgap states to reduce the bandgap, with the calculated bandgap change comparable to the experimental observation. Moreover, these states facilitate electron–hole separation in Cs<sub>2</sub>AgBiBr<sub>6</sub>, suppressing their recombination and, thus, extending the carrier lifetime, despite the reduced bandgap. Our results rationalize the experimental phenomena and provide crucial insights into the development of novel lead-free perovskite materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"27 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729130","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c02463
Piermarco Saraceno, Fabrizio Santoro, Lorenzo Cupellini
Among the peripheral antenna complexes of Photosystem I, Lhca4 exhibits the most striking signatures of low-lying exciton states, such as red-shifted absorption and fluorescence bands. These so-called “red forms” arise from strong coupling between locally excited (LE) and charge-transfer (CT) states within the a603-a609 chlorophyll (Chl) dimer. We employ ML-MCTDH quantum dynamics simulations and first-principles calculated Hamiltonians to investigate the CT mechanism between the two Chls. Our simulations reveal ultrafast (∼50 fs) population transfer, finely modulated by the protein environment via the LE–CT energy gap. Our analysis reveals the adiabatic and coherent nature of the process, providing mechanistic insight into the CT process in Lhca4. The system relaxes toward a coherent exciton-CT mixture with partial charge separation, a low lying state that still supports bright emission and energy transfer.
{"title":"Quantum Dynamics Simulations Reveal Ultrafast and Coherent Charge Transfer in the Lhca4 Antenna of Photosystem I","authors":"Piermarco Saraceno, Fabrizio Santoro, Lorenzo Cupellini","doi":"10.1021/acs.jpclett.5c02463","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02463","url":null,"abstract":"Among the peripheral antenna complexes of Photosystem I, <i>Lhca4</i> exhibits the most striking signatures of low-lying exciton states, such as red-shifted absorption and fluorescence bands. These so-called “red forms” arise from strong coupling between locally excited (LE) and charge-transfer (CT) states within the a603-a609 chlorophyll (Chl) dimer. We employ ML-MCTDH quantum dynamics simulations and first-principles calculated Hamiltonians to investigate the CT mechanism between the two Chls. Our simulations reveal ultrafast (∼50 fs) population transfer, finely modulated by the protein environment via the LE–CT energy gap. Our analysis reveals the adiabatic and coherent nature of the process, providing mechanistic insight into the CT process in <i>Lhca4</i>. The system relaxes toward a coherent exciton-CT mixture with partial charge separation, a low lying state that still supports bright emission and energy transfer.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"29 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729090","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}
Lanthanoid-antenna complexes are promising building blocks for quantum technologies, yet their potential in the condensed phase is often obscured by phonon-induced decoherence. This article reports the first one-color helium-tagging spectroscopic measurements of isolated [Ho(enpypa)]+ and [Yb(enpypa)]+ complexes (enpypa = ethylenediamine-pyridine-picolinic acid) at cryogenic temperatures, directly resolving their elusive 4f-4f excitations in the gas phase. For Ho3+, at least eight Stark-split multiplets are identified across the visible spectrum, while the Yb3+ complex exhibits a sharp 2F7/2 → 2F5/2 near-infrared manifold together with a hot band consistent with thermal equilibrium at 4 K. The UV-absorbing ligand shows depletion cross sections over two orders of magnitude larger than the lanthanoid-centered transitions, highlighting the sensitivity and dynamic range of our next-generation apparatus. These results establish cryogenic ion trap spectroscopy as a powerful tool for probing lanthanoid photophysics and pave the way for multicolor spectroscopic investigations of lanthanoid systems tailored for quantum information science.
{"title":"Direct Measurement of 4f-4f Transitions and Electronic Hot Bands in Lanthanoid-Antenna Complexes by Helium-Tagging Spectroscopy: Toward Molecular-Scale Trapped Ion Qubits.","authors":"Simran Baweja,Manfred M Kappes,Alexander Schäfer,Aigars Znotins,Roman Zielke,Christof Holzer,Timo Neumann,Christian Kruck,Michael Seitz","doi":"10.1021/acs.jpclett.5c03294","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03294","url":null,"abstract":"Lanthanoid-antenna complexes are promising building blocks for quantum technologies, yet their potential in the condensed phase is often obscured by phonon-induced decoherence. This article reports the first one-color helium-tagging spectroscopic measurements of isolated [Ho(enpypa)]+ and [Yb(enpypa)]+ complexes (enpypa = ethylenediamine-pyridine-picolinic acid) at cryogenic temperatures, directly resolving their elusive 4f-4f excitations in the gas phase. For Ho3+, at least eight Stark-split multiplets are identified across the visible spectrum, while the Yb3+ complex exhibits a sharp 2F7/2 → 2F5/2 near-infrared manifold together with a hot band consistent with thermal equilibrium at 4 K. The UV-absorbing ligand shows depletion cross sections over two orders of magnitude larger than the lanthanoid-centered transitions, highlighting the sensitivity and dynamic range of our next-generation apparatus. These results establish cryogenic ion trap spectroscopy as a powerful tool for probing lanthanoid photophysics and pave the way for multicolor spectroscopic investigations of lanthanoid systems tailored for quantum information science.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"224 1","pages":"13046-13053"},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728630","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c03195
Haiyi Huang, Juanjuan Zhang, Deping Hu, Ya-Jun Liu
In this study, we perform on-the-fly nonadiabatic molecular dynamics (NAMD) simulations for three molecular systems (ethylene, DMABN, and fulvene), which are suggested as molecular versions of the Tully models, with the trajectory surface hopping method based on the mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT). We employ several density functionals (CAM-B3LYP, M06-2X, BH&HLYP, and DTCAM-VAEE) in the MRSF-TDDFT calculations and compare the results with those obtained with the SA-CASSCF and MS-CASPT2 methods. For the ethylene molecule, the dynamics results obtained with MRSF-TDDFT compare very well with those obtained with MS-CASPT2, and the results with different functionals are similar. For the DMABN and fulvene molecules, the dynamics results with different functionals show certain differences, while the DTCAM-VAEE functional performs best among all functionals compared to MS-CASPT2. Moreover, for all molecules, MRSF-TDDFT outperforms SA-CASSCF for all functionals used in this work. We further explain the discrepancies of the dynamics results with different electronic structure methods through reaction pathway analysis. Overall, we strongly recommend the use of MRSF-TDDFT, especially with the DTCAM-VAEE functionals, in the NAMD simulations for complex molecular systems in the future, considering its good balance between accuracy and computational cost.
{"title":"Nonadiabatic Dynamics of the Molecular Tully Models with the Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory","authors":"Haiyi Huang, Juanjuan Zhang, Deping Hu, Ya-Jun Liu","doi":"10.1021/acs.jpclett.5c03195","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03195","url":null,"abstract":"In this study, we perform on-the-fly nonadiabatic molecular dynamics (NAMD) simulations for three molecular systems (ethylene, DMABN, and fulvene), which are suggested as molecular versions of the Tully models, with the trajectory surface hopping method based on the mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT). We employ several density functionals (CAM-B3LYP, M06-2X, BH&HLYP, and DTCAM-VAEE) in the MRSF-TDDFT calculations and compare the results with those obtained with the SA-CASSCF and MS-CASPT2 methods. For the ethylene molecule, the dynamics results obtained with MRSF-TDDFT compare very well with those obtained with MS-CASPT2, and the results with different functionals are similar. For the DMABN and fulvene molecules, the dynamics results with different functionals show certain differences, while the DTCAM-VAEE functional performs best among all functionals compared to MS-CASPT2. Moreover, for all molecules, MRSF-TDDFT outperforms SA-CASSCF for all functionals used in this work. We further explain the discrepancies of the dynamics results with different electronic structure methods through reaction pathway analysis. Overall, we strongly recommend the use of MRSF-TDDFT, especially with the DTCAM-VAEE functionals, in the NAMD simulations for complex molecular systems in the future, considering its good balance between accuracy and computational cost.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"143 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729093","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 : 2025-12-12DOI: 10.1021/acs.jpclett.5c03637
Mikhail R. Samatov, Dongyu Liu, Emir S. Amirov, Maria A. Bubnova, Andrey E. Abrameshin, Alexander S. Kramarenko, Pavel A. Troshin, Weibin Chu, Huanping Zhou, Oleg V. Prezhdo, Andrey S. Vasenko
Ion migration at grain boundaries (GBs) is a key issue leading to the performance degradation of metal halide perovskites (MHPs). Given the weak lattice interactions, the properties of MHPs are highly sensitive to external strain, which is inevitable in practical applications. Nevertheless, a fundamental understanding of the GB behavior under strain is still lacking. Using machine learning molecular dynamics, we demonstrate that uniaxial strain dictates both structural variation and ion migration at a CsPbBr3 GB. Tensile and strain-free conditions lead to grain sliding along the boundaries, creating versatile migration channels for all species. In contrast, compressive strain triggers lattice tilting within each grain and generates amorphous GB structures, blocking migration channels and ultimately quenching ion mobility. Our work elucidates the pivotal role of strain in determining the performance of MHPs and establishes compressive strain engineering as a promising strategy for enhancing their stability.
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