ACS Physical Chemistry Au最新文献

{"title":"How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol","authors":"Dennis F. Dinu*,&nbsp;Kemal Oenen,&nbsp;Jonas Schlagin,&nbsp;Maren Podewitz,&nbsp;Hinrich Grothe,&nbsp;Thomas Loerting and Klaus R. Liedl,&nbsp;","doi":"10.1021/acsphyschemau.4c0005310.1021/acsphyschemau.4c00053","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00053https://doi.org/10.1021/acsphyschemau.4c00053","url":null,"abstract":"<p >Unraveling methanol’s infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration. These experiments are accompanied by calculating wavenumbers involving anharmonicity and mode-coupling based on the vibrational configuration interaction approach. This allows for an unambiguous assignment of all fundamentals and resonances in the mid-infrared spectrum. An increasing degree of deuteration lifts resonances and aids in assigning bands uniquely. It also becomes evident that different notations typically used in chemistry or physics to describe molecular vibration from spectroscopy fail to describe the spectra appropriately. We highlight the shortcomings and suggest a more elaborate analysis using Sankey diagrams to unambiguously identify spectral features. Consequently, we demystify debated resonances occurring from various stretches and deformations of the methyl group.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"679–695 679–695"},"PeriodicalIF":3.7,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol.","authors":"Dennis F Dinu, Kemal Oenen, Jonas Schlagin, Maren Podewitz, Hinrich Grothe, Thomas Loerting, Klaus R Liedl","doi":"10.1021/acsphyschemau.4c00053","DOIUrl":"10.1021/acsphyschemau.4c00053","url":null,"abstract":"<p><p>Unraveling methanol's infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration. These experiments are accompanied by calculating wavenumbers involving anharmonicity and mode-coupling based on the vibrational configuration interaction approach. This allows for an unambiguous assignment of all fundamentals and resonances in the mid-infrared spectrum. An increasing degree of deuteration lifts resonances and aids in assigning bands uniquely. It also becomes evident that different notations typically used in chemistry or physics to describe molecular vibration from spectroscopy fail to describe the spectra appropriately. We highlight the shortcomings and suggest a more elaborate analysis using Sankey diagrams to unambiguously identify spectral features. Consequently, we demystify debated resonances occurring from various stretches and deformations of the methyl group.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"679-695"},"PeriodicalIF":3.7,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613289/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142780962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spinodal Decomposition by a Two-Step Procedure for Nano Porous Silica","authors":"Zuyi Zhang*,&nbsp;","doi":"10.1021/acsphyschemau.4c0006010.1021/acsphyschemau.4c00060","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00060https://doi.org/10.1021/acsphyschemau.4c00060","url":null,"abstract":"<p >The phase separation of the Na₂O–B₂O₃–SiO₂ system was explored both theoretically and experimentally in order to attain a spinodal structure having a narrowed periodic distance (&lt;70 nm) with the porosity being kept at ∼60%. The phase separation was dealt with by two stages: an initial thermodynamic process of spinodal decomposition and a latter growth of the spinodal structure. The initial structural development was related to the interfacial energy and the change in free energy caused by phase separation. For the latter growth, a mathematical model was proposed to explain the kinetics by incorporating the effect of the inverse-square law in the diffusion of SiO₂, and a basic relation of <i></i><math><msup><mrow><mi>d</mi></mrow><mrow><mn>3</mn></mrow></msup><mo>−</mo><msup><mrow><msub><mrow><mi>d</mi></mrow><mrow><mn>0</mn></mrow></msub></mrow><mrow><mn>3</mn></mrow></msup><mo>∝</mo><mi>t</mi></math> (<i>d</i>: average periodic distance; <i>t</i>: time) was successfully derived. The phase separation was carried out accordingly by two steps: first for the phase separation forming durable silica skeletons at lower temperatures and second for the new equilibrium at the elevated temperature and the subsequent growth of the phase-separated structure. It was proven that the addition of Al₂O₃ in the glasses decreased the interfacial energy, leading to small periodic distances and the rapid establishment of the durable silica skeletons. In the two-step process, the fraction of borate-rich phase increased, and the structure grew depending on a modified period of time.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"696–706 696–706"},"PeriodicalIF":3.7,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00060","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spinodal Decomposition by a Two-Step Procedure for Nano Porous Silica.","authors":"Zuyi Zhang","doi":"10.1021/acsphyschemau.4c00060","DOIUrl":"10.1021/acsphyschemau.4c00060","url":null,"abstract":"<p><p>The phase separation of the Na₂O-B₂O₃-SiO₂ system was explored both theoretically and experimentally in order to attain a spinodal structure having a narrowed periodic distance (<70 nm) with the porosity being kept at ∼60%. The phase separation was dealt with by two stages: an initial thermodynamic process of spinodal decomposition and a latter growth of the spinodal structure. The initial structural development was related to the interfacial energy and the change in free energy caused by phase separation. For the latter growth, a mathematical model was proposed to explain the kinetics by incorporating the effect of the inverse-square law in the diffusion of SiO₂, and a basic relation of (<i>d</i>: average periodic distance; <i>t</i>: time) was successfully derived. The phase separation was carried out accordingly by two steps: first for the phase separation forming durable silica skeletons at lower temperatures and second for the new equilibrium at the elevated temperature and the subsequent growth of the phase-separated structure. It was proven that the addition of Al₂O₃ in the glasses decreased the interfacial energy, leading to small periodic distances and the rapid establishment of the durable silica skeletons. In the two-step process, the fraction of borate-rich phase increased, and the structure grew depending on a modified period of time.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"696-706"},"PeriodicalIF":3.7,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613344/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142781070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study of Photoselectivity in Linear Conjugated Chromophores Using the XMS-CASPT2 Method.","authors":"Saumik Sen, Xavier Deupi","doi":"10.1021/acsphyschemau.4c00065","DOIUrl":"10.1021/acsphyschemau.4c00065","url":null,"abstract":"<p><p>Photoisomerization, the structural alteration of molecules upon absorption of light, is crucial for the function of biological chromophores such as retinal in opsins, proteins vital for vision and other light-sensitive processes. The intrinsic selectivity of this isomerization process (i.e., which double bond in the chromophore is isomerized) is governed by both the inherent properties of the chromophore and its surrounding environment. In this study, we employ the extended multistate complete active space second-order perturbation theory (XMS-CASPT2) method to investigate photoisomerization selectivity in linear conjugated chromophores, focusing on two simple molecular models resembling retinal. By analyzing electronic energies, intramolecular charge separation, and conical intersection topographies in the gas phase, we show that the photoproduct formed by rotation around the double bond near the Schiff base is energetically favored. The topographic differences at the conical intersections leading to different photoproducts reveal differences in photodynamics. In multiphoton excitation, the primary photoproduct typically reverts to the initial configuration rather than rotating around a different double bond. Our study offers new insights into the photodynamics of photoisomerizing double bonds in π-conjugated chromophores. We anticipate that our findings will provide valuable perspectives for advancing the understanding of biological chromophores and for designing efficient photochemical switches with applications in molecular electronics and phototherapy.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"736-749"},"PeriodicalIF":3.7,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613312/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142780998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study of Photoselectivity in Linear Conjugated Chromophores Using the XMS-CASPT2 Method","authors":"Saumik Sen*,&nbsp; and ,&nbsp;Xavier Deupi*,&nbsp;","doi":"10.1021/acsphyschemau.4c0006510.1021/acsphyschemau.4c00065","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00065https://doi.org/10.1021/acsphyschemau.4c00065","url":null,"abstract":"<p >Photoisomerization, the structural alteration of molecules upon absorption of light, is crucial for the function of biological chromophores such as retinal in opsins, proteins vital for vision and other light-sensitive processes. The intrinsic selectivity of this isomerization process (i.e., which double bond in the chromophore is isomerized) is governed by both the inherent properties of the chromophore and its surrounding environment. In this study, we employ the extended multistate complete active space second-order perturbation theory (XMS-CASPT2) method to investigate photoisomerization selectivity in linear conjugated chromophores, focusing on two simple molecular models resembling retinal. By analyzing electronic energies, intramolecular charge separation, and conical intersection topographies in the gas phase, we show that the photoproduct formed by rotation around the double bond near the Schiff base is energetically favored. The topographic differences at the conical intersections leading to different photoproducts reveal differences in photodynamics. In multiphoton excitation, the primary photoproduct typically reverts to the initial configuration rather than rotating around a different double bond. Our study offers new insights into the photodynamics of photoisomerizing double bonds in π-conjugated chromophores. We anticipate that our findings will provide valuable perspectives for advancing the understanding of biological chromophores and for designing efficient photochemical switches with applications in molecular electronics and phototherapy.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"736–749 736–749"},"PeriodicalIF":3.7,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00065","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystal Lattice-Induced Stress modulates Photoinduced Jahn-Teller Distortion Dynamics.","authors":"Vandana Tiwari, Marcus Gallagher-Jones, Hyein Hwang, Hong-Guang Duan, Angus I Kirkland, R J Dwayne Miller, Ajay Jha","doi":"10.1021/acsphyschemau.4c00047","DOIUrl":"10.1021/acsphyschemau.4c00047","url":null,"abstract":"<p><p>Efficient photoredox chemical transformations are essential to the development of novel, cost-effective, and environmentally friendly synthetic methodologies. The concept of the entatic state in bioinorganic catalysis proposes that a preorganized structural configuration can reduce the energy barriers associated with chemical reactions. This concept provides one of the guiding principles to enhance catalytic efficiency by maintaining high-energy conformations close to the reaction's transition state. Copper(I)-based photocatalysts, recognized for their low toxicity and highly negative oxidation potentials, are of particular interest in entasis studies. In this study, we explore the impact of entasis caused by stress induced by the surrounding lattice on the excited state dynamics of a prototypical copper(I)-based photocatalyst in a single crystal form. Using femtosecond broadband transient absorption spectroscopy, we show that triplet state formation from the entactic state is faster (∼3.9 ps) in crystals compared with solution (∼11.3 ps). The observed faster intersystem crossing in crystals hints toward the possible existence of distorted square planar geometry with higher spin-orbit coupling at the minima of the S₁ state. We further discuss the influence of entasis on vibrationally coherent photoinduced Jahn-Teller distortions. Our findings reveal the photophysical properties of the copper complex under lattice-induced stress, which can be extended to enhance the broader applicability of the entatic state concept in other transition metal systems. Understanding how environmental stress-induced geometric constraints within crystal lattices affect photochemical behavior opens avenues for designing more efficient photocatalytic systems based on transition metals, potentially enhancing their applicability to sustainable chemical synthesis.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"660-668"},"PeriodicalIF":3.7,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11613236/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142780732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystal Lattice-Induced Stress modulates Photoinduced Jahn–Teller Distortion Dynamics","authors":"Vandana Tiwari,&nbsp;Marcus Gallagher-Jones,&nbsp;Hyein Hwang,&nbsp;Hong-Guang Duan,&nbsp;Angus I. Kirkland,&nbsp;R. J. Dwayne Miller* and Ajay Jha*,&nbsp;","doi":"10.1021/acsphyschemau.4c0004710.1021/acsphyschemau.4c00047","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00047https://doi.org/10.1021/acsphyschemau.4c00047","url":null,"abstract":"<p >Efficient photoredox chemical transformations are essential to the development of novel, cost-effective, and environmentally friendly synthetic methodologies. The concept of the entatic state in bioinorganic catalysis proposes that a preorganized structural configuration can reduce the energy barriers associated with chemical reactions. This concept provides one of the guiding principles to enhance catalytic efficiency by maintaining high-energy conformations close to the reaction’s transition state. Copper(I)-based photocatalysts, recognized for their low toxicity and highly negative oxidation potentials, are of particular interest in entasis studies. In this study, we explore the impact of entasis caused by stress induced by the surrounding lattice on the excited state dynamics of a prototypical copper(I)-based photocatalyst in a single crystal form. Using femtosecond broadband transient absorption spectroscopy, we show that triplet state formation from the entactic state is faster (∼3.9 ps) in crystals compared with solution (∼11.3 ps). The observed faster intersystem crossing in crystals hints toward the possible existence of distorted square planar geometry with higher spin–orbit coupling at the minima of the S₁ state. We further discuss the influence of entasis on vibrationally coherent photoinduced Jahn–Teller distortions. Our findings reveal the photophysical properties of the copper complex under lattice-induced stress, which can be extended to enhance the broader applicability of the entatic state concept in other transition metal systems. Understanding how environmental stress-induced geometric constraints within crystal lattices affect photochemical behavior opens avenues for designing more efficient photocatalytic systems based on transition metals, potentially enhancing their applicability to sustainable chemical synthesis.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"660–668 660–668"},"PeriodicalIF":3.7,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00047","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Roundabout Mechanism of Ion–Molecule Nucleophilic Substitution Reactions","authors":"Xiangyu Wu,&nbsp;Fei Ying,&nbsp;Hongyi Wang,&nbsp;Li Yang,&nbsp;Jiaxu Zhang and Jing Xie*,&nbsp;","doi":"10.1021/acsphyschemau.4c0006110.1021/acsphyschemau.4c00061","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00061https://doi.org/10.1021/acsphyschemau.4c00061","url":null,"abstract":"<p >Roundabout (RA) is an important indirect mechanism for gas-phase X^– + CH₃Y → XCH₃ + Y^– S_N2 reactions at a high collision energy. It refers to the rotation of the CH₃-group by half or multiple circles upon the collision of incoming nucleophiles before substitution takes place. The RA mechanism was first discovered in the Cl^– + CH₃I S_N2 reaction to explain the energy transfer observed in crossed molecular beam imaging experiments in 2008. Since then, the RA mechanism and its variants have been observed not only in multiple C-centered S_N2 reactions, but also in N-centered S_N2 reactions, proton transfer reactions, and elimination reactions. This work reviewed recent studies on the RA mechanism and summarized the characteristics of RA mechanisms in terms of variant types, product energy partitioning, and product velocity scattering angle distribution. RA mechanisms usually happen at small impact parameters and tend to couple with other mechanisms at relatively low collision energy, and the available energy of roundabout trajectories is primarily partitioned to internal energy. Factors that affect the importance of the RA mechanism were analyzed, including the type of leaving group and nucleophile, collision energy, and microsolvation. A massive leaving group and relatively high collision energy are prerequisite for the occurrence of the roundabout mechanism. Interestingly, when reacting with CH₃I, the importance of RA mechanisms follows an order of Cl^– &gt; HO^– &gt; F^–, and such a nucleophile dependence was attributed to the difference in proton affinity and size of the nucleophile.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"581–592 581–592"},"PeriodicalIF":3.7,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Roundabout Mechanism of Ion–Molecule Nucleophilic Substitution Reactions","authors":"Xiangyu Wu, Fei Ying, Hongyi Wang, Li Yang, Jiaxu Zhang, Jing Xie","doi":"10.1021/acsphyschemau.4c00061","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00061","url":null,"abstract":"Roundabout (RA) is an important indirect mechanism for gas-phase X^– + CH₃Y → XCH₃ + Y^– S_N2 reactions at a high collision energy. It refers to the rotation of the CH₃-group by half or multiple circles upon the collision of incoming nucleophiles before substitution takes place. The RA mechanism was first discovered in the Cl^– + CH₃I S_N2 reaction to explain the energy transfer observed in crossed molecular beam imaging experiments in 2008. Since then, the RA mechanism and its variants have been observed not only in multiple C-centered S_N2 reactions, but also in N-centered S_N2 reactions, proton transfer reactions, and elimination reactions. This work reviewed recent studies on the RA mechanism and summarized the characteristics of RA mechanisms in terms of variant types, product energy partitioning, and product velocity scattering angle distribution. RA mechanisms usually happen at small impact parameters and tend to couple with other mechanisms at relatively low collision energy, and the available energy of roundabout trajectories is primarily partitioned to internal energy. Factors that affect the importance of the RA mechanism were analyzed, including the type of leaving group and nucleophile, collision energy, and microsolvation. A massive leaving group and relatively high collision energy are prerequisite for the occurrence of the roundabout mechanism. Interestingly, when reacting with CH₃I, the importance of RA mechanisms follows an order of Cl^– &gt; HO^– &gt; F^–, and such a nucleophile dependence was attributed to the difference in proton affinity and size of the nucleophile.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}