化学•材料最新文献

{"title":"Toward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations","authors":"Jonathan R. Mannouch, Aaron Kelly","doi":"10.1021/acs.jpclett.4c02418","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02418","url":null,"abstract":"The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat electronic coherence. However, the most popular and practical nonadiabatic molecular dynamics techniques, Tully’s fewest-switches surface hopping and Ehrenfest mean-field dynamics, are unable to describe the dynamics proceeding from an initial electronic coherence. While such issues are not encountered with the analogous coupled-trajectory algorithms or numerically exact quantum dynamics methods, applying such techniques necessarily comes with a higher computational cost. Here we show that a correct description of initial electronic coherence can indeed be achieved using independent-trajectory methods derived from the semiclassical mapping formalism. The key is the introduction of an initial sampling over the electronic phase space and a means of incorporating phase interference between trajectories, both of which are naturally achieved when working within the semiclassical mapping framework.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610034","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}

{"title":"Surface Plasmons in Two-Dimensional MXenes","authors":"Calvin Raab, Janek Rieger, Atreyie Ghosh, Joseph L. Spellberg, Sarah B. King","doi":"10.1021/acs.jpclett.4c02882","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02882","url":null,"abstract":"MXenes, a class of layered two-dimensional transition metal carbides and nitrides, exhibit excellent optoelectronic properties and show promise for fields ranging from photonics and communications to energy storage and catalysis. Some members of the MXene family are metallic and exhibit large in-plane conductivity, making them possibly suited for 2D plasmonics. The highly variable chemical structure of MXenes offers a broad chemical space to tune material properties for plasmonic applications, including plasmon-enhanced catalysis, surface-enhanced Raman spectroscopy (SERS), and electromagnetic shielding. However, this synthetic complexity has also presented several roadblocks in the process of moving MXene plasmonics into applications. For example, in the prototypical MXene Ti₃C₂T_<i>x</i>, there remains disagreement over the bulk plasmon energy and the assignment of a prominent resonance around 1.7 eV. We discuss fundamental models and theories of plasmon physics and apply these models to MXenes in order to clarify some of these problems. We outline the potential for hyperbolic plasmons in MXenes and propose new avenues for MXene photonics research.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610039","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}

{"title":"Raman Spectroscopic Observation of Electrolyte-Dependent Oxygen Evolution Reaction Intermediates in Nickel-Based Electrodes","authors":"Tomohiro Fukushima, Kenko Tsuchimoto, Nobuaki Oyamada, Daiki Sato, Hiro Minamimoto, Kei Murakoshi","doi":"10.1021/acs.jpcc.4c06732","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06732","url":null,"abstract":"Oxygen evolution reaction (OER) is the counterpart in hydrogen production by water electrolysis. Further challenges have been required to bypass the energy consumption processes in the OER. It is still important to unveil the OER intermediates toward effective green hydrogen production. In this study, we conducted in situ Raman observation of the OER intermediates over Ni nanohole-array electrodes in the various electrolyte conditions. Ni nanohole-array electrodes were prepared with interference exposure methods. Intense Raman peaks were observed from Ni–OH, Ni-OOH, and active oxygen species as the OER intermediates. The OER behavior can be classified with the reactants, such as OH^– and H₂O. The presented study demonstrates the importance of the electrolyte for the designing active OER catalysis for the next generation energy society.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142610047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Prediction of Redox Potentials for Ac, Th, and Pa in Aqueous Solution.","authors":"Felipe R Dutra, João G F Romeu, David A Dixon","doi":"10.1021/acs.jpca.4c05693","DOIUrl":"10.1021/acs.jpca.4c05693","url":null,"abstract":"<p><p>Density functional theory in conjunction with small core pseudopotentials and the associated basis sets was used to calculate potentials for multiple redox couples, covering a range of oxidation states for Ac (0 to III), Th (0 to IV), and Pa (0 to V) in aqueous solution. Solvation effects were incorporated using a supermolecule-continuum approach, with 30 water molecules representing two solvation shells, and the COSMO and SMD implicit solvation models. The calculated geometries for Ac(III), Th(IV), and Pa(V) were in reasonable agreement with the available experimental data. Using the COSMO model with the B3LYP functional, the calculated redox potentials were within ±0.2 V from experiment for most redox couples. Several pathways were explored for the Pa(V/IV) redox couple for different forms of Pa(V) and Pa(IV). Most Pa(V/IV) redox couples have very similar potentials, ranging from 0 to -0.4 V up to a pH of 1.4. At pH = 1.4, the potentials shift to values that are more negative than -0.7 V, reflecting the growing unfavorable nature of the redox process at higher pH levels. The calculated values for An(III/II) potentials were consistent with prior estimates and the available experimental data. The predicted redox potentials for An(II/I) were highly negative, as expected. For An(I/0) potentials, Th and Pa exhibited positive values, contrasting with the negative values calculated for Ac. The An^+m/An(0) potentials agreed better with the experimental data when using the COSMO solvation model as compared to the SMD model.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542918","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}

{"title":"Optical Quantum Control of the Electron Transfer Reactions in Protein Flavodoxin.","authors":"Na Liu, Yifei Zhang, Xi Wang, Kangwei Niu, Faming Lu, Jie Chen, Dongping Zhong","doi":"10.1021/acs.jpcb.4c04254","DOIUrl":"10.1021/acs.jpcb.4c04254","url":null,"abstract":"<p><p>The optical quantum control has been successfully applied in modulating biological processes such as energy transfer and bond isomerization. Among the reactions in realizing biological functions, the electron transfer (ET) process is fundamental; hence, the quantum control over such an ET reaction is of far-reaching significance. Here, we realized optical quantum control over ultrafast ET processes in a protein, flavodoxin, by applying various chirped excitation pulses. We observed the wavepacket dynamics within a dephasing time of less than 1 ps. Within this time window, we found that the ultrafast photoinduced ET reaction can be controlled by different chirped excitations with a rate change by a factor of about 2. Furthermore, the control effect is propagated into the subsequent ultrafast back ET reaction, showing a variation of the BET dynamics with different excitation chirps. The underlying mechanism is the initial wavepacket dynamics; the differently prepared wavepackets with chirped excitation evolve along various pathways, resulting in the changes of ET rates. The successful demonstration of optical quantum control of ultrafast biological ET is significant and opens a new avenue to explore the quantum control of real biological ET reactions.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556670","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}

{"title":"Transferable and Interpretable Prediction of Site-Specific Dehydrogenation Reaction Rate Constants with NMR Spectra.","authors":"Yanbo Li, Fenfen Ma, Zhandong Wang, Xin Chen","doi":"10.1021/acs.jpclett.4c02647","DOIUrl":"10.1021/acs.jpclett.4c02647","url":null,"abstract":"<p><p>Accurate and efficient determination of site-specific reaction rate constants over a wide temperature range remains challenging, both experimentally and theoretically. Taking the dehydrogenation reaction as an example, our study addresses this issue by an innovative combination of machine learning techniques and cost-effective NMR spectra. Through descriptor screening, we identified a minimal set of NMR chemical shifts that can effectively determine reaction rate constants. The constructed model performs exceptionally well on theoretical data sets and demonstrates impressive generalization capabilities, extending from small molecules to larger ones. Furthermore, this model shows outstanding performance when applied to limited experimental data sets, highlighting its robust applicability and transferability. Utilizing the Sure Independence Screening and Sparsifying Operator (SISSO) algorithm, we also present an interpretable rate constant-temperature-NMR (k-T-NMR) relationship with a mathematical formula. This study reveals the great potential of combining machine learning with easily accessible spectroscopic descriptors in the study of reaction kinetics, enabling the rapid determination of reaction rate constants and promoting our understanding of reactivity.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566369","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}

{"title":"<i>In Silico</i> Structural Comparison of Aromatic and Aliphatic Chiral Peptoid Oligomers.","authors":"Rakshit Kumar Jain, Carol K Hall, Erik E Santiso","doi":"10.1021/acs.jpcb.4c06577","DOIUrl":"10.1021/acs.jpcb.4c06577","url":null,"abstract":"<p><p>Atomistic simulations of peptoids have the capability to predict structure-property relationships, depending on the accuracy of the associated force field. This work presents an addendum to the CGenFF-NTOID peptoid force field for aliphatic side chains. We develop parameters for two aliphatic side chains, R_<i>N</i>1-tertiary butylethyl glycine (<i>r1tbe</i>) and S_<i>N</i>1-tertiary butylethyl glycine (<i>s1tbe</i>). Enhanced sampled (well-tempered metadynamics) atomistic simulations are performed using CGenFF-NTOID to determine the monomer structural preferences for these side chains. The free energy minima attained through these simulations are compared with structural observations obtained from experiments. We also compare the structural preferences of aliphatic <i>s1tbe</i> and aromatic S_<i>N</i>1-naphthylethyl glycine (<i>s1ne</i>). This is done through parallel bias metadynamics on monomers and pentamers of <i>s1tbe</i> and <i>s1ne</i>. The structural observations through simulations are also compared with available experimental metrics of the dihedral angles and pitch. The pentamer minima structures are also compared with <i>ab initio</i> optimized structures, which show excellent agreement. This comparison illustrates alternatives to aromatic side chains that can be used to stabilize peptoid secondary structures. The developed parameters help to increase the diversity of peptoid side chains available for materials discovery through computational studies.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566428","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}

{"title":"Unique Applications of <i>para</i>-Hydrogen Matrix Isolation to Spectroscopy and Astrochemistry.","authors":"Isabelle Weber, Prasad Ramesh Joshi, David T Anderson, Yuan-Pern Lee","doi":"10.1021/acs.jpclett.4c02733","DOIUrl":"10.1021/acs.jpclett.4c02733","url":null,"abstract":"<p><p>Cryogenic solid <i>para</i>-hydrogen (<i>p</i>-H₂) exhibits pronounced quantum effects, enabling unique experiments that are typically not possible in noble-gas matrices. The diminished cage effect facilitates the production of free radicals via <i>in situ</i> photolysis or photoinduced reactions. Electron bombardment during deposition readily produces protonated and hydrogenated species, such as polycyclic aromatic hydrocarbons, that are important in astrochemistry. In addition, quantum diffusion delocalizes hydrogen atoms in solid <i>p</i>-H₂, allowing efficient H atom reactions with astrochemical species and introducing new concepts in astrochemical models. Some H atom reactions display anomalous temperature behaviors, highlighting the rich chemistry in <i>p</i>-H₂. The investigation on quantum diffusion of heavier atoms and molecules is also important for our understanding of the chemistry in interstellar ice. Additionally, matrix shifts of electronic transitions of polycyclic aromatic hydrocarbons in <i>p</i>-H₂ are less divergent than those in solid Ne such that systematic measurements in <i>p</i>-H₂ might help in the assignment of diffuse interstellar bands.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142581035","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}

{"title":"<i>N</i>-Carbazolyl π-Radical and Its Antiaromatic Nitrenium Ion: A Threshold Photoelectron Spectroscopic Study.","authors":"Mayank Saraswat, Adrian Portela-Gonzalez, Enrique Mendez-Vega, Wolfram Sander, Patrick Hemberger","doi":"10.1021/acs.jpca.4c05855","DOIUrl":"10.1021/acs.jpca.4c05855","url":null,"abstract":"<p><p>Understanding the structure and properties of heterocyclic radicals and their cations is crucial for elucidating reaction mechanisms as they serve as versatile synthetic intermediates. In this work, the <i>N</i>-carbazolyl radical <b>1</b> was generated via pyrolysis and characterized using photoion mass-selected threshold photoelectron spectroscopy coupled with tunable vacuum-ultraviolet synchrotron radiation. The <i>N</i>-centered radical <b>1</b> is classified as a π-radical (²B₁), with the unpaired electron found to be delocalized over the central five-membered ring of the carbazole. Adiabatic ionization energies corresponding to the transition from radical <b>1</b> to its singlet <b>1</b>⁺(¹A₁) and triplet <b>1</b>⁺(³B₂) cations were determined to be 7.70 ± 0.03 and 8.14 ± 0.03 eV, respectively. The antiaromatic nitrenium ion <b>1</b>^<b>+</b> exhibits a singlet ground state with an experimental singlet-triplet energy gap (Δ<i>E</i>_S-T) of -0.44 eV (10.1 kcal/mol), in very good agreement with theory. <i>N</i>-centered radicals are found to have a higher ionization energy than their <i>C</i>-centered analogues due to stabilization of the singly occupied molecular orbital.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491175","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}

{"title":"Comparisons between the Direct and Indirect Effect of 1.5 keV X-rays and 0-30 eV Electrons on DNA: Base Lesions, Stand Breaks, Cross-Links, and Cluster Damages.","authors":"Yingxia Gao, Yanfang Dong, Xuran Wang, Wenyue Su, Pierre Cloutier, Yi Zheng, Léon Sanche","doi":"10.1021/acs.jpcb.4c02799","DOIUrl":"10.1021/acs.jpcb.4c02799","url":null,"abstract":"<p><p>The interaction of low energy electrons (LEEs; 1-30 eV) with genomic material can induce multiple types of damage that may cause the loss of genetic information, mutations, genome instability, and cell death. For all damages measurable by electrophoresis, we provide the first complete set of <i>G</i>-values (yield of a specific product per energy deposited) induced in plasmid DNA by the direct and indirect effects of LEEs (<i>G</i>_LEE) and 1.5 keV X-rays (<i>G</i>_X) under identical conditions. Low energy photoelectrons are produced via X-rays incident on a tantalum (Ta) substrate covered with DNA and placed in a chamber filled with nitrogen at atmospheric pressure, under four different humidity levels, ranging from dry conditions to full hydration (Γ = 2.5 to Γ = 33, where Γ is the number of water molecules/nucleotide). Damage yields are measured as a function of X-ray fluence and humidity. <i>G</i>_LEE values are between 2 and 27 times larger than those for X-rays. At Γ = 2.5 and 33, <i>G</i>_LEE values for double strand breaks are 27 and 16 times larger than <i>G</i>_X, respectively. The indirect effect contributes ∼50% to the total damage. These <i>G</i>-values allow quantification of potentially lethal lesions composed of strand breaks and/or base damages in the presence of varying amounts of water, i.e., closer to cellular conditions.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491191","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}