Dongyu Liu, Bayan Amer Abzakh, Elena A. Kazakova, Dmitrii A. Abrameshin, Pavel A. Troshin, Run Long and Andrey S. Vasenko*,
{"title":"Wave Function Localization Reduces the Bandgap of Disordered Double Perovskite Cs2AgBiBr6","authors":"Dongyu Liu, Bayan Amer Abzakh, Elena A. Kazakova, Dmitrii A. Abrameshin, Pavel A. Troshin, Run Long and Andrey S. Vasenko*, ","doi":"10.1021/acs.jpclett.4c0294610.1021/acs.jpclett.4c02946","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02946https://doi.org/10.1021/acs.jpclett.4c02946","url":null,"abstract":"<p >Double perovskite Cs<sub>2</sub>AgBiBr<sub>6</sub> is a promising alternative to lead-based perovskites with excellent stability and attractive optoelectronic properties. However, a relatively large bandgap severely limits its performance in many applications such as solar cells and photodetectors. It has been reported that a random distribution of Ag and Bi atoms in Cs<sub>2</sub>AgBiBr<sub>6</sub> effectively reduces its bandgap without introducing dopants or impurities, while the mechanism remains unclear. Here, using density functional theory calculations, we demonstrate that the Ag–Bi disorder in Cs<sub>2</sub>AgBiBr<sub>6</sub> generates localized electronic states as band edges to regulate the bandgap. The disordered structures segregate Ag and Bi atoms in the lattice, and the formed homoatomic clusters lead to wave function localization. Moreover, the bandgap decrease exhibits a non-monotonic dependence on the degree of disorder. Our results are comparable with experimental observations and provide crucial insights into understanding the order–disorder transition in double perovskites.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11268–11274 11268–11274"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640981","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}
Yanbo Li*, Fenfen Ma, Zhandong Wang and Xin Chen*,
{"title":"Transferable and Interpretable Prediction of Site-Specific Dehydrogenation Reaction Rate Constants with NMR Spectra","authors":"Yanbo Li*, Fenfen Ma, Zhandong Wang and Xin Chen*, ","doi":"10.1021/acs.jpclett.4c0264710.1021/acs.jpclett.4c02647","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02647https://doi.org/10.1021/acs.jpclett.4c02647","url":null,"abstract":"<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":"15 45","pages":"11282–11290 11282–11290"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640828","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":"Selective Methods Promote Protein Solid-State NMR","authors":"Bin Han, Jun Yang* and Zhengfeng Zhang*, ","doi":"10.1021/acs.jpclett.4c0284110.1021/acs.jpclett.4c02841","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02841https://doi.org/10.1021/acs.jpclett.4c02841","url":null,"abstract":"<p >Solid-state nuclear magnetic resonance (ssNMR) is indispensable for studying the structures, dynamics, and interactions of insoluble proteins in native or native-like environments. While ssNMR includes numerous nonselective techniques for general analysis, it also provides various selective methods that allow for the extraction of precise details about proteins. This perspective highlights three key aspects of selective methods: selective signals of protein segments, selective recoupling, and site-specific insights into proteins. These methods leverage protein topology, labeling strategies, and the tailored manipulation of spin interactions through radio frequency (RF) pulses, significantly promoting the field of protein ssNMR. With ongoing advancements in higher magnetic fields and faster magic angle spinning (MAS), there remains an ongoing need to enhance the selectivity and efficiency of selective ssNMR methods, facilitating deeper atomic-level insights into complex biological systems.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11300–11311 11300–11311"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640819","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}
Bin Wang, Paul Geerlings, Farnaz Heidar-Zadeh, Paul W. Ayers and Frank De Proft*,
{"title":"Slope of the Delocalization Function Is Proportional to Analytical Hardness","authors":"Bin Wang, Paul Geerlings, Farnaz Heidar-Zadeh, Paul W. Ayers and Frank De Proft*, ","doi":"10.1021/acs.jpclett.4c0226310.1021/acs.jpclett.4c02263","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02263https://doi.org/10.1021/acs.jpclett.4c02263","url":null,"abstract":"<p >Conceptual Density Functional Theory (CDFT) has been extended beyond its traditional role in elucidating chemical reactivity to the development of density functional theory methods, e.g., the investigation of the delocalization error. This delocalization error causes the dependence of the energy on the number of electrons (<i>N</i>) to deviate from its exact piecewise linear behavior, an error which is the basis of many well-known limitations of commonly used density-functional approximations (DFAs). Following our previous work on the analytical hardness η<sup>±</sup> for pure functionals, we extend its application to hybrid and range-separated functionals. A comparison is made between the analytical hardness and the slope of the delocalization function introduced by Hait and Head-Gordon. Our results show that there is a linear relationship between its slope and the analytical hardness. An approximate scheme is presented to construct the energy vs <i>N</i> curve without fractional occupation number calculations. The extension to densities is discussed.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11259–11267 11259–11267"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640984","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}
Benhui Yang*, Chen Qu, J. M. Bowman, Dongzheng Yang, Hua Guo, N. Balakrishnan, R. C. Forrey and P. C. Stancil*,
{"title":"Inelastic Triatom-Atom Quantum Close-Coupling Dynamics in Full Dimensionality: All Rovibrational Mode Quenching of Water Due to the H Impact on a Six-Dimensional Potential Energy Surface","authors":"Benhui Yang*, Chen Qu, J. M. Bowman, Dongzheng Yang, Hua Guo, N. Balakrishnan, R. C. Forrey and P. C. Stancil*, ","doi":"10.1021/acs.jpclett.4c0286510.1021/acs.jpclett.4c02865","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02865https://doi.org/10.1021/acs.jpclett.4c02865","url":null,"abstract":"<p >The rovibrational level populations, and subsequent emission in various astrophysical environments, are driven by inelastic collision processes. The available rovibrational rate coefficients for water have been calculated using a number of approximations. We present a numerically exact calculation for the rovibrational quenching for all water vibrational modes due to collisions with atomic hydrogen. The scattering theory implements a quantum close-coupling (CC) method on a high level ab initio six-dimensional (6D) potential energy surface (PES). Total rovibrational quenching cross sections for excited bending levels were compared with earlier results on a 4D PES with the rigid-bender close-coupling (RBCC) approximation. General agreement between 6D-CC and 4D-RBCC calculations are found, but differences are evident including the energy and amplitude of low-energy orbiting resonances. Quenching cross sections from the symmetric and asymmetric stretch modes are provided for the first time. The current 6D-CC calculation provides accurate inelastic data needed for astrophysical modeling.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11312–11319 11312–11319"},"PeriodicalIF":4.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c02865","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640821","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}
Andreas Schiller*, Sandra Jenatsch, Balthasar Blülle, Miguel Angel Torre Cachafeiro, Firouzeh Ebadi, Nasim Kabir, Mostafa Othman, Christian Michael Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Wolfgang Tress and Beat Ruhstaller,
{"title":"Assessing the Influence of Illumination on Ion Conductivity in Perovskite Solar Cells","authors":"Andreas Schiller*, Sandra Jenatsch, Balthasar Blülle, Miguel Angel Torre Cachafeiro, Firouzeh Ebadi, Nasim Kabir, Mostafa Othman, Christian Michael Wolff, Aïcha Hessler-Wyser, Christophe Ballif, Wolfgang Tress and Beat Ruhstaller, ","doi":"10.1021/acs.jpclett.4c0240310.1021/acs.jpclett.4c02403","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02403https://doi.org/10.1021/acs.jpclett.4c02403","url":null,"abstract":"<p >Whether illumination influences the ion conductivity in lead-halide perovskite solar cells containing iodide halides has been an ongoing debate. Experiments to elucidate the presence of a photoconductive effect require special devices or measurement techniques and neglect possible influences of the enhanced electronic charge concentrations. Here, we assess the electronic-ionic charge transport using drift-diffusion simulations and show that the well-known increase in capacitance at low frequencies under illumination is caused by electronic currents that are amplified due to the screening of the alternating electric field by the ions. We propose a novel characterization technique to detect a potential photoinduced increase in ionic conductivity based on capacitance measurements on fully integrated devices. The method is applied to a range of perovskite solar cells with different active layer materials. Remarkably, all measured samples show a clear signature of photoenhanced ion conductivity, posing fundamental questions on the underlying nature of the photosensitive mechanism.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11252–11258 11252–11258"},"PeriodicalIF":4.8,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c02403","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640742","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}
Zhendong Feng, Qingnan Wang, Pengfei Zhang, Guanna Li, Jijie Wang, Zhaochi Feng* and Can Li*,
{"title":"Generation of Surface Ga-H Hydride and Reactivity toward CO2","authors":"Zhendong Feng, Qingnan Wang, Pengfei Zhang, Guanna Li, Jijie Wang, Zhaochi Feng* and Can Li*, ","doi":"10.1021/acs.jpclett.4c0285410.1021/acs.jpclett.4c02854","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02854https://doi.org/10.1021/acs.jpclett.4c02854","url":null,"abstract":"<p >Hydrogen adsorption on gallium oxide was investigated by in situ infrared (IR) spectroscopy over a temperature range of 30–450 °C. Both hydroxyl groups and Ga-H hydrides with a pair of characteristic bands at 3685 (3532) cm<sup>–1</sup> and 2011 (1988) cm<sup>–1</sup> were detected on the surface gallium oxide. The formation and stability of surface Ga-H hydrides were found to be highly dependent on the temperature of H<sub>2</sub> dissociation. Through a combination of density functional theory (DFT) calculations and isotopic experiments, a mechanism involving both heterolytic and homolytic pathways for hydrogen dissociation was proposed for the generation of Ga-H hydrides. Furthermore, the reactivity of surface Ga-H hydrides was explored by their interactions with various probe molecules such as carbon dioxide, oxygen, and nitrogen. A potential reaction mechanism involving the attraction between nucleophilic hydrogen and positively charged intermediates was suggested during those hydrogenations.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11194–11199 11194–11199"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640818","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":"Overlooked Role of Electrostatic Interactions in HER Kinetics on MXenes: Beyond the Conventional Descriptor ΔG ∼ 0 to Identify the Real Active Site","authors":"Xiang Huang, Xiangting Hu, Jiong Wang and Hu Xu*, ","doi":"10.1021/acs.jpclett.4c0258810.1021/acs.jpclett.4c02588","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02588https://doi.org/10.1021/acs.jpclett.4c02588","url":null,"abstract":"<p >Understanding the atomic-level mechanism of the hydrogen evolution reaction (HER) on MXene materials is crucial for developing affordable HER catalysts, while their complex surface terminations present a substantial challenge. Herein, employing constant-potential grand canonical density functional theory calculations, we elucidate the reaction kinetics of the HER on MXenes with various surface terminations by taking experimentally reported Mo<sub>2</sub>C as a prototype. We observe a contradictory scenario on Mo<sub>2</sub>C MXene when using conventional thermodynamic descriptor Δ<i>G</i><sub>H*</sub> (hydrogen binding energy). Both competing surface phases that emerge close to the equilibrium potential meet the Δ<i>G</i><sub>H*</sub> ∼ 0 criterion, while they exhibit distinctly different reaction kinetics. Contrary to previous studies that identified surface *O species as active sites, our research reveals that these *O sites are kinetically inert for producing H<sub>2</sub> but are easily reduced to H<sub>2</sub>O. Consequently, the surface Mo atoms, exposed from the rapid reduction of the surface *O species, serve as the actual active sites catalyzing the HER via the Volmer–Heyrovsky mechanism, as confirmed by experimental studies. Our findings highlight the overlooked role of electrostatic repulsion in HER kinetics, a factor not captured by thermodynamic descriptor Δ<i>G</i><sub>H*</sub>. This work provides new insights into the HER mechanism and emphasizes the importance of kinetic investigations for a comprehensive understanding of the HER.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11200–11208 11200–11208"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640873","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}
Lingyun Wan, Jie Liu*, Zhenyu Li and Jinlong Yang*,
{"title":"Hybrid Hamiltonian Simulation for Excitation Dynamics","authors":"Lingyun Wan, Jie Liu*, Zhenyu Li and Jinlong Yang*, ","doi":"10.1021/acs.jpclett.4c0262410.1021/acs.jpclett.4c02624","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02624https://doi.org/10.1021/acs.jpclett.4c02624","url":null,"abstract":"<p >Hamiltonian simulation is one of the most anticipated applications of quantum computing. Quantum circuit depth for implementing Hamiltonian simulation is commonly time dependent using Trotter-Suzuki product formulas so that long time quantum dynamic simulations (QDSs) become impratical for near-term quantum processors. Hamiltonian simulation based on Cartan decomposition (CD) provides an appealing scheme for QDSs with fixed-depth circuits, while it is limited to a time-independent Hamiltonian. In this work, we generalize this CD-based Hamiltonian simulation algorithm for studying time-dependent systems by combining it with variational quantum algorithms. The time-dependent and time-independent parts of the Hamiltonian are treated by using variational and CD-based Hamiltonian simulation algorithms, respectively. As such, this hybrid Hamiltonian simulation requires only fixed-depth quantum circuits to handle time-dependent cases while maintaining a high accuracy. We apply this new algorithm to study the response of spin and molecular systems to δ-kick electric fields and obtain accurate spectra for these excitation processes.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11234–11243 11234–11243"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640867","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}
Xiao Zhang, Qianqian Liang, Qing Song, Yang Liu, Yue Wang*, Yonghua Chen, Deli Li* and Wei Huang*,
{"title":"Electrical Doping Regulation of Carrier Recombination Enhances the Perovskite Solar Cell Efficiency beyond 28%","authors":"Xiao Zhang, Qianqian Liang, Qing Song, Yang Liu, Yue Wang*, Yonghua Chen, Deli Li* and Wei Huang*, ","doi":"10.1021/acs.jpclett.4c0282610.1021/acs.jpclett.4c02826","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02826https://doi.org/10.1021/acs.jpclett.4c02826","url":null,"abstract":"<p >With the power conversion efficiency (PCE) of perovskite solar cells (PSCs) exceeding 26.7%, achieving further enhancements in device performance has become a key research focus. Here, we investigate the impact of electrical doping in the perovskite layer using the drift-diffusion equation-based device physics model, coupled with a self-developed equivalent circuit model. Our results demonstrate that electrical doping can increase the PCE from 24.78% to >28%. In-depth theoretical analysis reveals that these improvements in performance are driven by the modulation of carrier recombination processes through doping, leading to significant increases in the open-circuit voltage and fill factor. Additionally, we explore the influence of physical parameters on device performance. Our study identifies an optimal doping concentration range from 1.0 × 10<sup>17</sup> to 1.0 × 10<sup>19</sup> cm<sup>–3</sup> and a transport layer mobility of >0.01 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>. This work provides a theoretical foundation for the development of ultra-high-performance PSCs through targeted electrical doping strategies.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11224–11233 11224–11233"},"PeriodicalIF":4.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640939","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}