The Journal of Physical Chemistry Letters最新文献_第5页

Symmetry Breaking around Aqueous Ammonia Revealed in Nitrogen K-edge X-ray Absorption

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-27 DOI: 10.1021/acs.jpclett.4c03625

Michael Odelius, Sarai Dery Folkestad, Thanit Saisopa, Yuttakarn Rattanachai, Wutthigrai Sailuam, Hayato Yuzawa, Nobuhiro Kosugi, Alexander C. Paul, Henrik Koch, Denis Céolin

{"title":"Symmetry Breaking around Aqueous Ammonia Revealed in Nitrogen K-edge X-ray Absorption","authors":"Michael Odelius, Sarai Dery Folkestad, Thanit Saisopa, Yuttakarn Rattanachai, Wutthigrai Sailuam, Hayato Yuzawa, Nobuhiro Kosugi, Alexander C. Paul, Henrik Koch, Denis Céolin","doi":"10.1021/acs.jpclett.4c03625","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03625","url":null,"abstract":"Nitrogen K-edge X-ray absorption (XA) spectroscopy of aqueous ammonia reveals a splitting in the main-edge, which through theoretical modeling is shown to be related to symmetry breaking in hydrogen bonding. The XA main-edge of NH3 is formed by a pair of degenerate core-excitations into extended molecular orbitals. In aqueous solution, these form an antibonding mixture with orbitals of the surrounding water molecules. Although the spectral response to distortions is complex, we show that the degeneracy of the core-excitations is lifted by asymmetry in hydrogen bond donation (NH···O). A quantitative relation between asymmetry in the hydration shell and splitting in the main-edge of the nitrogen K-edge XA spectrum is established from systematic symmetry breaking in well-defined cluster models and through molecular dynamics sampling of simulated XA spectra of aqueous ammonia. The finding indicates that XA spectroscopy is a sensitive probe of asymmetry in solvation also around functional groups in biomolecules.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"61 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713583","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}

引用次数: 0

Physical Chemistry of Water Microdroplets

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c00434

Agustín J. Colussi

引用次数: 0

Nonempirical Adiabatic Connection Correlation Functional from Hartree–Fock Orbitals

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.4c0359310.1021/acs.jpclett.4c03593

Lucian A. Constantin, Eduardo Fabiano and Fabio Della Sala*,

{"title":"Nonempirical Adiabatic Connection Correlation Functional from Hartree–Fock Orbitals","authors":"Lucian A. Constantin, Eduardo Fabiano and Fabio Della Sala*, ","doi":"10.1021/acs.jpclett.4c0359310.1021/acs.jpclett.4c03593","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03593https://doi.org/10.1021/acs.jpclett.4c03593","url":null,"abstract":"We present a nonempirical strategy to construct a correlation functional rooted in the Møller–Plesset (MP) adiabatic connection (AC) formalism for the strong-interaction regime, which satisfies both the weak- and strong-interaction limits and describes accurately the uniform electron gas (UEG) model. The functional is based on Hartree–Fock (HF) orbitals and employs only the UEG and helium atom as model systems; thus, it can be considered a nonempirical and nonlinear generalization of post-HF approaches based on the second-order perturbation theory (MP2) correlation. The functional describes the correlation of atoms with 1 mHa/electron accuracy, and it is also accurate for jellium surface energies. Accurate tests using a nearly complete basis set on diverse systems and properties (atomization/interaction energies, dispersion forces, and ionization potentials) have shown an excellent performance of the functional that corrects the MP2 overbinding without error cancellation. The present investigation can open the way for the development of a new generation of post-HF functionals based on nonlinear MP2 contributions and strong-correlation ingredients.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 13","pages":"3378–3388 3378–3388"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c03593","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Crystallization-Induced Emission Enhancement or Quenching? Elucidating the Mechanism behind Using Single-Molecule-Based Versatile Crystals

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c00774

Yutong Shang, Yalei Ma, Qiangbazhuoma, Baimaquzhen, Liping Ding, Jing Liu, Shiwei Yin, Rong Miao, Yu Fang

{"title":"Crystallization-Induced Emission Enhancement or Quenching? Elucidating the Mechanism behind Using Single-Molecule-Based Versatile Crystals","authors":"Yutong Shang, Yalei Ma, Qiangbazhuoma, Baimaquzhen, Liping Ding, Jing Liu, Shiwei Yin, Rong Miao, Yu Fang","doi":"10.1021/acs.jpclett.5c00774","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00774","url":null,"abstract":"It is challenging to predict optical properties of fluorescent dyes, especially in the crystalline state, owing to the uncertainty in conformation, packing, and coupling. Herein, we elucidate the decisive role of molecular conformation and molecular packing in the fluorescence emissions of some crystalline materials based on experimental results and theoretical calculations. Two homologous fluorophores (Ph-MP and Ph-HP) were synthesized, and they both exhibited interesting crystallization-induced emission enhancement and quenching. Although the homologues show almost the same fluorescence behavior in the solid state, on–off emission of their crystals depends upon different factors. Emission of the Ph-MP crystals is governed by the twisted intramolecular charge transfer effect, while emission of the Ph-HP crystals relied on π–π stacking. Based on this understanding, application of single-molecule-based versatile crystals in information encryption was demonstrated. It is believed that the evidence and unveiled mechanism for the effect of crystallization on emission will contribute to development in high-performance luminescent materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713766","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}

引用次数: 0

Crystallization-Induced Emission Enhancement or Quenching? Elucidating the Mechanism behind Using Single-Molecule-Based Versatile Crystals

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c0077410.1021/acs.jpclett.5c00774

Yutong Shang, Yalei Ma, Qiangbazhuoma, Baimaquzhen, Liping Ding, Jing Liu, Shiwei Yin, Rong Miao* and Yu Fang,

{"title":"Crystallization-Induced Emission Enhancement or Quenching? Elucidating the Mechanism behind Using Single-Molecule-Based Versatile Crystals","authors":"Yutong Shang, Yalei Ma,  Qiangbazhuoma,  Baimaquzhen, Liping Ding, Jing Liu, Shiwei Yin, Rong Miao* and Yu Fang, ","doi":"10.1021/acs.jpclett.5c0077410.1021/acs.jpclett.5c00774","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00774https://doi.org/10.1021/acs.jpclett.5c00774","url":null,"abstract":"It is challenging to predict optical properties of fluorescent dyes, especially in the crystalline state, owing to the uncertainty in conformation, packing, and coupling. Herein, we elucidate the decisive role of molecular conformation and molecular packing in the fluorescence emissions of some crystalline materials based on experimental results and theoretical calculations. Two homologous fluorophores (Ph-MP and Ph-HP) were synthesized, and they both exhibited interesting crystallization-induced emission enhancement and quenching. Although the homologues show almost the same fluorescence behavior in the solid state, on–off emission of their crystals depends upon different factors. Emission of the Ph-MP crystals is governed by the twisted intramolecular charge transfer effect, while emission of the Ph-HP crystals relied on π–π stacking. Based on this understanding, application of single-molecule-based versatile crystals in information encryption was demonstrated. It is believed that the evidence and unveiled mechanism for the effect of crystallization on emission will contribute to development in high-performance luminescent materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 13","pages":"3389–3396 3389–3396"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758836","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}

引用次数: 0

Ambipolar Behavior of Hematite Surface Induced by Water Adsorption Revealed under Environmental Conditions

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c0030510.1021/acs.jpclett.5c00305

Pierre-Marie Deleuze, Bruno Domenichini, Hélène Magnan, Mathieu G. Silly, Antoine Barbier, Sylvie Bourgeois and Céline Dupont*,

{"title":"Ambipolar Behavior of Hematite Surface Induced by Water Adsorption Revealed under Environmental Conditions","authors":"Pierre-Marie Deleuze, Bruno Domenichini, Hélène Magnan, Mathieu G. Silly, Antoine Barbier, Sylvie Bourgeois and Céline Dupont*, ","doi":"10.1021/acs.jpclett.5c0030510.1021/acs.jpclett.5c00305","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00305https://doi.org/10.1021/acs.jpclett.5c00305","url":null,"abstract":"In this work, we determine the electronic structure and charge carrier dynamics of α-Fe2O3(0001) ultrathin film deposited on Pt(111) as a function of water pressure by combined near ambient pressure–time-resolved photoelectron spectroscopy (NAP-TR-PES) measurements and DFT calculations. Under ultrahigh vacuum (UHV) α-Fe2O3 exhibits the expected typical n-type semiconductor behavior with a surface photovoltage (SPV) shift of 31 meV. Surprisingly, when exposed to water a completely different comportment appears. At a partial pressure of water of PH2O = 0.02 hPa, a much smaller SPV (7 meV) appears that is shifted in the opposite direction, which is thus characteristic of a p-type semiconductor. Finally, at PH2O > 0.1 hPa, SPV is canceled, which is consistent with a layer of metallic nature. DFT calculations explain these experimental findings well as originating from a modification of the surface structure and electronic properties of the layer consecutive to water adsorption. It is shown that the Fermi level position in the band gap of hematite depends on the quantity of adsorbed water, giving rise to the ambipolar behavior of the surface, which is able to transport both negative and positive charges when exposed to the appropriate water pressure.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 13","pages":"3371–3377 3371–3377"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758839","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}

引用次数: 0

Ambipolar Behavior of Hematite Surface Induced by Water Adsorption Revealed under Environmental Conditions

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c00305

Pierre-Marie Deleuze, Bruno Domenichini, Hélène Magnan, Mathieu G. Silly, Antoine Barbier, Sylvie Bourgeois, Céline Dupont

{"title":"Ambipolar Behavior of Hematite Surface Induced by Water Adsorption Revealed under Environmental Conditions","authors":"Pierre-Marie Deleuze, Bruno Domenichini, Hélène Magnan, Mathieu G. Silly, Antoine Barbier, Sylvie Bourgeois, Céline Dupont","doi":"10.1021/acs.jpclett.5c00305","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00305","url":null,"abstract":"In this work, we determine the electronic structure and charge carrier dynamics of α-Fe2O3(0001) ultrathin film deposited on Pt(111) as a function of water pressure by combined near ambient pressure–time-resolved photoelectron spectroscopy (NAP-TR-PES) measurements and DFT calculations. Under ultrahigh vacuum (UHV) α-Fe2O3 exhibits the expected typical n-type semiconductor behavior with a surface photovoltage (SPV) shift of 31 meV. Surprisingly, when exposed to water a completely different comportment appears. At a partial pressure of water of PH2O = 0.02 hPa, a much smaller SPV (7 meV) appears that is shifted in the opposite direction, which is thus characteristic of a p-type semiconductor. Finally, at PH2O > 0.1 hPa, SPV is canceled, which is consistent with a layer of metallic nature. DFT calculations explain these experimental findings well as originating from a modification of the surface structure and electronic properties of the layer consecutive to water adsorption. It is shown that the Fermi level position in the band gap of hematite depends on the quantity of adsorbed water, giving rise to the ambipolar behavior of the surface, which is able to transport both negative and positive charges when exposed to the appropriate water pressure.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"88 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703624","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}

引用次数: 0

Nonempirical Adiabatic Connection Correlation Functional from Hartree–Fock Orbitals

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.4c03593

Lucian A. Constantin, Eduardo Fabiano, Fabio Della Sala

{"title":"Nonempirical Adiabatic Connection Correlation Functional from Hartree–Fock Orbitals","authors":"Lucian A. Constantin, Eduardo Fabiano, Fabio Della Sala","doi":"10.1021/acs.jpclett.4c03593","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03593","url":null,"abstract":"We present a nonempirical strategy to construct a correlation functional rooted in the Møller–Plesset (MP) adiabatic connection (AC) formalism for the strong-interaction regime, which satisfies both the weak- and strong-interaction limits and describes accurately the uniform electron gas (UEG) model. The functional is based on Hartree–Fock (HF) orbitals and employs only the UEG and helium atom as model systems; thus, it can be considered a nonempirical and nonlinear generalization of post-HF approaches based on the second-order perturbation theory (MP2) correlation. The functional describes the correlation of atoms with 1 mHa/electron accuracy, and it is also accurate for jellium surface energies. Accurate tests using a nearly complete basis set on diverse systems and properties (atomization/interaction energies, dispersion forces, and ionization potentials) have shown an excellent performance of the functional that corrects the MP2 overbinding without error cancellation. The present investigation can open the way for the development of a new generation of post-HF functionals based on nonlinear MP2 contributions and strong-correlation ingredients.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"183 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713763","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}

引用次数: 0

Physical Chemistry of Water Microdroplets

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-26 DOI: 10.1021/acs.jpclett.5c0043410.1021/acs.jpclett.5c00434

Agustín J. Colussi*,

{"title":"Physical Chemistry of Water Microdroplets","authors":"Agustín J. Colussi*, ","doi":"10.1021/acs.jpclett.5c0043410.1021/acs.jpclett.5c00434","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00434https://doi.org/10.1021/acs.jpclett.5c00434","url":null,"abstract":"Orders-of-magnitude reaction accelerations and the formation of H2O2 in aerosolized water microdroplets are in search of explanation. These processes are not overall spontaneous as generally assumed because they are preceded by the forced aerosolization of water. Nor are they caused by internal electric fields because the electrical activation of chemical reactions requires external static fields vectorially aligned with transition state dipoles. The formation of H2O2 is enabled by the partial dehydration of HO– and H+ ions in low-density interfacial water, a process that raises their free energies of formation and lifts the endoergicity of the prerequisite electron transfer HO– + H+ = HO• + H• in bulk water. The lack of unimolecular reaction accelerations suggests the accelerations of bimolecular reactions are due to the higher frequencies of molecular encounters, fewer transition state recrossings, and smaller entropy losses for expanding solvent cavities to hold their transition states in interfacial vs bulk water.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 13","pages":"3366–3370 3366–3370"},"PeriodicalIF":4.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758791","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}

引用次数: 0

Enhancing the Photoexcited Carrier Spin Relaxation Lifetime in CsPbBr3 Perovskite Quantum Dots by 208Pb Isotope Enrichment

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-03-25 DOI: 10.1021/acs.jpclett.5c00123

Vivien L. Cherrette, David Zeitz, Mariam Khvichia, Jason K. Cooper, Yuan Ping, Jeremy Lake Barnett, Jin Z. Zhang

{"title":"Enhancing the Photoexcited Carrier Spin Relaxation Lifetime in CsPbBr3 Perovskite Quantum Dots by 208Pb Isotope Enrichment","authors":"Vivien L. Cherrette, David Zeitz, Mariam Khvichia, Jason K. Cooper, Yuan Ping, Jeremy Lake Barnett, Jin Z. Zhang","doi":"10.1021/acs.jpclett.5c00123","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00123","url":null,"abstract":"CsPbBr3 perovskite quantum dot (PQD) films enriched with 208Pb (I = 0) or 207Pb (I = 1/2) isotope were used to study the effect of nuclear spin on the photoexcited carrier spin relaxation using circularly polarized femtosecond transient absorption spectroscopy at 293 and 77 K. At 293 K, the short carrier spin relaxation lifetimes of 208Pb-enriched PQDs (2.0 ps) and natPb PQDs (0.70 ps) indicate that electron–phonon interactions dominate. At 77 K, the 207Pb-enriched PQD carrier spin relaxation lifetime was not detectible within the instrumental limit (<0.30 ps). However, the carrier spin relaxation lifetime increased to 5.0 ps for natPb PQDs and 170 ps for 208Pb-enriched PQDs. The dramatic increase in the 208Pb-enriched PQD carrier spin relaxation lifetime suggests that decreasing the concentration of 207Pb in the PQDs can reduce spin decoherence from nuclear spin–carrier spin coupling and enhance the lifetime.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"23 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695787","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}

引用次数: 0