The Journal of Physical Chemistry A最新文献

{"title":"Investigation of the Structure and Optical Properties of Polymethine-Based NIR-II Fluorophores Using Many-Body Perturbation Theory: GW-BSE Approaches.","authors":"Hengquan Guo, Nguyet N T Pham, Jong S Park, Seung Geol Lee","doi":"10.1021/acs.jpca.4c06115","DOIUrl":"10.1021/acs.jpca.4c06115","url":null,"abstract":"<p><p>Fluorescence imaging is a widely used technique for detecting pathophysiological microenvironments and guiding fluorescence-guided therapy owing to its noninvasiveness, high spatiotemporal resolution, ease of operation, and real-time monitoring capabilities. In particular, NIR-II materials are promising for fluorescence imaging applications because they exhibit reduced light scattering and absorption by biological tissues, enabling deeper imaging with improved spatial resolution and contrast compared to visible or first near-infrared imaging. NIR-II materials refer to those that emit in the second near-infrared region of the electromagnetic spectrum, spanning wavelengths from approximately 1000 to 1700 nm. The emission peaks of organic fluorophores within the NIR-II window are of particular interest due to their minimal biotoxicity, in vivo biocompatibility, and biodegradability. In this study, we investigated a new series of NIR-II fluorescent polymethine-based dyes and their NIR-II absorption properties using density functional theory and the GW-BSE approximation. Our calculated maximum absorption peak under the GW-BSE approximation showed good agreement with experimental results, demonstrating the potential of these dyes for NIR-II fluorescence imaging applications.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491181","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":"Prediction of the Infrared Absorbance Intensities and Frequencies of Hydrocarbons: A Message Passing Neural Network Approach.","authors":"Maliheh Shaban Tameh, Veaceslav Coropceanu, Thomas A R Purcell, Jean-Luc Brédas","doi":"10.1021/acs.jpca.4c06745","DOIUrl":"10.1021/acs.jpca.4c06745","url":null,"abstract":"<p><p>Accurately and efficiently predicting the infrared (IR) spectra of a molecule can provide insights into the structure-properties relationships of molecular species, which has led to a proliferation of machine learning tools designed for this purpose. However, earlier studies have focused primarily on obtaining normalized IR spectra, which limits their potential for a comprehensive analysis of molecular behavior in the IR range. For instance, to fully understand and predict the optical properties, such as the transparency characteristics, it is necessary to predict the molar absorptivity IR spectra instead. Here, we propose a graph-based communicative message passing neural network algorithm that can predict both the peak positions and absolute intensities corresponding to density functional theory calculated molar absorptivities in the IR domain. By modifying existing spectral loss functions, we show that our method is able to predict with DFT-accuracy level the IR molar absorptivities of a series of hydrocarbons containing up to ten carbon atoms and apply the model to a set of larger molecules. We also compare the predicted spectra with those generated by the direct message passing neural network. The results suggest that both algorithms demonstrate similar predictive capabilities for hydrocarbons, indicating that either model could be effectively used in future research on spectral prediction for such systems.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520267","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":"Reduced Scaling Correlated Natural Transition Orbitals for Multilevel Coupled Cluster Calculations.","authors":"Sarai Dery Folkestad, Henrik Koch","doi":"10.1021/acs.jpca.4c06271","DOIUrl":"10.1021/acs.jpca.4c06271","url":null,"abstract":"<p><p>Multilevel coupled cluster theory offers reduced scaling computation of intensive properties in systems that are too large for standard coupled cluster calculations. A significant benefit of the multilevel coupled cluster framework is the possibility of calculating intensive properties that are not tightly localized if an appropriate set of active orbitals is used. Correlated natural transition orbitals (CNTOs) are tailored to describe excitation processes. For multilevel coupled cluster singles and doubles (MLCCSD) and singles and perturbative doubles (MLCC2) calculations, the construction of CNTOs generally becomes the computational bottleneck. Here, we demonstrate how CNTOs can be obtained with <math><mi>O</mi><mrow><mo>(</mo><msup><mrow><mi>N</mi></mrow><mrow><mn>3</mn></mrow></msup><mo>)</mo></mrow></math> operations, eliminating the <math><mi>O</mi><mrow><mo>(</mo><msup><mrow><mi>N</mi></mrow><mrow><mn>5</mn></mrow></msup><mo>)</mo></mrow></math>-scaling steps involved in the original approach. This reduction in scaling moves the bottleneck of MLCC2 and MLCCSD calculations from the active orbital space preparation to the MLCC2 and MLCCSD equations with <math><mi>O</mi><mrow><mo>(</mo><msup><mrow><mi>N</mi></mrow><mrow><mn>4</mn></mrow></msup><mo>)</mo></mrow></math>-scaling.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11551955/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142491187","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}

{"title":"An Increase in the Rigidity of the Environment Favors MLCT over the MC State in [Ru(bpy)₂(Nicotine)₂](Cl)₂: A Case Study of Photolabile Ligands.","authors":"Mohini Semwal, Nikita Vashistha, Sven Rau, Benjamin Dietzek-Ivanšić","doi":"10.1021/acs.jpca.4c04914","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c04914","url":null,"abstract":"<p><p>Ru(II)-complexes with photolabile ligands find a wide range of applications, e.g., in drug release and in the design of light-responsive interfaces. While light-driven ligand loss has been studied mechanistically in detail for complexes in solution, comparably few studies are present that investigate the process in a material context, i.e., in a rigid environment and in the absence of solvent. This paper adds to this underrepresented perspective by studying the excited-state dynamics of [Ru(bpy)₂(nicotine)₂] (Cl)₂ (<b>Ru-nico</b>) as a model system in poly(methyl methacrylate) (PMMA) and polyacrylonitrile (PAN) matrices. Femtosecond transient absorption spectroscopy and time-resolved emission spectroscopy are employed to monitor the photodissociation of labile nicotine ligands in polymer environments. Photoexcitation within the metal-to-ligand charge transfer (MLCT) band leads to transient dissociation of the nicotine ligand when the complex is dissolved in water. However, optical excitation of the ¹MLCT transition of the complexes embedded in polymer matrices does not result in photodissociation, likely due to the rigidity of the environment, which cannot solvate the undercoordinated complex after ligand dissociation and the dissociated ligand. These insights shed light on the role of the local environment when considering the photophysics of ligand loss from Ru(II)-polypyridyl complexes and, hence, their use in the light-activation of reactive molecular components in materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142575440","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":"Enhancing Photogenerated Radical Pair Properties in Donor-Chromophore-Acceptor Systems for Quantum Information Applications.","authors":"Paige J Brown, Yunfan Qiu, Elisabeth I Latawiec, Brian T Phelan, Nikolai A Tcyrulnikov, Jonathan R Palmer, Matthew D Krzyaniak, Sebastian M Kopp, Yuheng Huang, Ryan M Young, Michael R Wasielewski","doi":"10.1021/acs.jpca.4c05015","DOIUrl":"10.1021/acs.jpca.4c05015","url":null,"abstract":"<p><p>We report on new donor-chromophore-acceptor triads <b>BDX-ANI-NDI</b> and <b>BDX-ANI-xy-NDI</b> where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-<i>d</i>;4,5-<i>d</i>]bis[1,3]dioxole, the ANI chromophore is 4-(<i>N</i>-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a <i>p</i>-methoxyaniline (MeOAn) as the donor. BDX^•<b>+</b> has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn^<b>•+</b>. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (<i>J</i>) for <b>BDX</b>^<b>•+</b><b>-ANI-NDI</b>^<b>•-</b> and <b>BDX</b>^<b>•+</b><b>-ANI-xy-NDI</b>^<b>•-</b> at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that <b>BDX</b>^<b>•+</b><b>-ANI-xy-NDI</b>^<b>•-</b> has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of <i>J</i>. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453487","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":"New Insight into Quantity-Dependent Self-Assembly Pattern of Light Levitating Droplet Clusters.","authors":"Pengcheng Jiang, Yijing Yang, Xun Zhu, Dingding Ye, Yang Yang, Hong Wang, Liang An, Alexander A Fedorets, Qiang Liao, Rong Chen, Michael Nosonovsky","doi":"10.1021/acs.jpca.4c06443","DOIUrl":"10.1021/acs.jpca.4c06443","url":null,"abstract":"<p><p>It has been reported that the self-assembly pattern of light levitating droplet clusters above the hot gas-liquid interface is dependent on the quantity of droplets. However, the already-reported theoretical explanation of the quantity-dependent self-assembly pattern cannot work well when the quantity of the light levitating droplet exceeds 15. Herein, we propose a new theoretical perspective to understand the self-assembly of a light levitating droplet cluster by referring to the classical densest packing problem of identical rigid circles in a larger circle with the introduction of the minimum total potential energy principle. Amazingly, the theoretical results obtained by this new approach agree well with experimental results, even though the quantity of the light levitating droplet is up to 142. This study deepens our understanding of the quantity-dependent self-assembly pattern of the light levitating droplet clusters and provides significant inspiration for other analogous self-assembly phenomena.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453499","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":"OH Radical Oxidation of Organosulfates in the Atmospheric Aqueous Phase.","authors":"Daniel T Gweme, Sarah A Styler","doi":"10.1021/acs.jpca.4c02877","DOIUrl":"10.1021/acs.jpca.4c02877","url":null,"abstract":"<p><p>Organosulfates (OS, ROSO₃^-), ubiquitous constituents of atmospheric particulate matter (PM), influence both the physicochemical and climatic properties of PM. Although the formation pathways of OS have been extensively researched, only a few studies have investigated the atmospheric fate of this class of compounds. Here, to better understand the reactivity and transformation of OS under cloudwater- and aerosol-relevant conditions, we investigate the hydroxyl radical (OH) oxidation bimolecular rate constants (<i>k</i>_OS+OH^II) and products of five atmospherically relevant OS as a function of pH and ionic strength: methyl sulfate (MeS), ethyl sulfate (EtS), propyl sulfate (PrS), hydroxyacetone sulfate (HaS) and phenyl sulfate (PhS). Our results show that OS are oxidized by OH with <i>k</i>_OS+OH^II between 10⁸ - 10⁹ M^-1 s^-1, which corresponds to atmospheric lifetimes of minutes in aqueous aerosol to days in cloudwater. We find that <i>k</i>_OS+OH^II increases with carbon chain length (MeS < EtS < PrS) and aromaticity (PrS < PhS), but does not depend on solution pH (2, 9). In addition, we find that whereas the OH reactivity of the aliphatic OS studied here decreases by ∼2× with increasing ionic strength (0-15 M), the reactivity of PhS decreases by ∼10×. The oxidation of EtS and PrS produced organic peroxides (ROOH) as first-generation oxidation products, which subsequently photolyzed; the oxidation of PhS resulted in hydroxylated aromatic products. These results highlight the need for inclusion of OS loss pathways in atmospheric models, and suggest caution in using ambient OS concentration measurements alone to estimate their production rates.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453500","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":"Describing the Disulfide Bond: From the Density Functional Theory and Back through the \"Lego Brick\" Approach.","authors":"Silvia Alessandrini, Hexu Ye, Malgorzata Biczysko, Cristina Puzzarini","doi":"10.1021/acs.jpca.4c05198","DOIUrl":"10.1021/acs.jpca.4c05198","url":null,"abstract":"<p><p>Selected molecular species containing the disulfide bond, RSSR, have been considered, these ranging from hydrogen disulfide, H₂S₂ (R = H), to diphenyl disulfide with R = C₆H₅. The aim of this work is two-fold: (i) to investigate different computational approaches in order to derive accurate equilibrium structures at an affordable cost, (ii) to employ the results from the first goal in order to benchmark cheaper methodologies rooted in the density functional theory. Among the strategies used for the accurate geometrical determinations, the semiexperimental approach has been exploited in combination with a reduced-dimensionality VPT2 model, without however obtaining satisfactory results. Instead, the so-called \"Lego brick\" approach turned out to be very effective despite the flexibility of the systems investigated. Concerning the second target of this work, the focus was mainly on the S-S bond and the structural parameters related to it. Among those tested, PBE0(-D3BJ), M06-2X(-D3) and DSD-PBEP86-D3BJ have been found to be the best-performing functionals.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453485","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":"Ozone Doping and Negative Temperature Response in the Explosion Limits of Ethylene-Oxygen Mixtures.","authors":"Jianhang Li, Chenyu Li, Wenkai Liang, Wenhu Han, Chung K Law","doi":"10.1021/acs.jpca.4c04778","DOIUrl":"10.1021/acs.jpca.4c04778","url":null,"abstract":"<p><p>In this work, effects of ozone (O₃) addition on ethylene-oxygen (C₂H₄-O₂) mixtures are computationally studied through the explosion limit profiles. The results show that the addition of minute quantities of ozone (with a mole fraction of 0.06% in the oxidizer) shifts the explosion limit of the C₂H₄-O₃-O₂ mixtures to the low-temperature regime. Further increases in the ozone concentration gradually strengthen the negative temperature coefficient (NTC) behavior at the second limit. That is because the explosion limit is primarily controlled by the ethylene ozonolysis reaction, and both the sensitivity analysis and chemical reaction rate perturbation method reveal specific kinetic reasons. Furthermore, it is shown that with the increasing equivalence ratio, the explosion limit curve with minute ozone addition rotates counterclockwise around a crossover point, while the explosion limit curve becomes complicated and the NTC behavior appears on the second limit with larger quantities of ozone addition. Furthermore, the effects of dilutions of nitrogen (N₂), argon (Ar), carbon dioxide (CO₂), and water (H₂O) on the explosion limits are also studied. To elucidate the different wall elimination effects of different explosion limit regimes, the impacts of surface reactions of six radicals (H, O, OH, HO₂, H₂O₂, and HCO) have been examined and the dominant radicals are found to be H and HO₂. The H radicals significantly influence the first explosion limit, while the HO₂ radicals impact the entire explosion limit.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453502","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":"Theoretical Investigation of the Reaction of O(¹D) with Formamide.","authors":"Desiree Bates, Brian J Esselman, Chase P Schultz, Susanna L Widicus Weaver","doi":"10.1021/acs.jpca.4c05611","DOIUrl":"10.1021/acs.jpca.4c05611","url":null,"abstract":"<p><p>Carbamic acid (H₂NCOOH) is a small organic molecule that is terrestrially unstable in condensed phases under ambient conditions but could survive in the low densities and temperatures of the interstellar medium. In this work, the reaction of formamide (H₂NCOH) and electronically excited oxygen atoms in the ¹D state, namely, O(¹D), has been investigated computationally to determine the feasibility of carbamic acid production. Geometries for carbamic acid and other potential reaction products have been calculated, as well as all pertinent transition states. In addition, harmonic and anharmonic frequency calculations were performed to determine quartic and sextic centrifugal distortion constants for all products. This work enables spectroscopic predictions that can guide the experimental search for carbamic acid. Presented here are the calculations, geometries, molecular constants, and spectral predictions for possible products of the reaction between formamide and O(¹D), as well as a discussion of which products are favored.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142453433","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}