化学•材料最新文献

{"title":"\"Best\" Iterative Coupled-Cluster Triples Model? More Evidence for 3CC.","authors":"Nakul K Teke, Ajay Melekamburath, Bimal Gaudel, Edward F Valeev","doi":"10.1021/acs.jpca.4c04667","DOIUrl":"10.1021/acs.jpca.4c04667","url":null,"abstract":"<p><p>To follow up on the unexpectedly good performance of several coupled-cluster models with approximate inclusion of 3-body clusters [Rishi, V.; Valeev, E. F. <i>J. Chem. Phys.</i> 2019, 151, 064102.] we performed a more complete assessment of the 3CC method [Feller, D. . <i>J. Chem. Phys.</i> 2008, 129, 204105.] for accurate computational thermochemistry in the standard HEAT framework. New spin-integrated implementation of the 3CC method applicable to closed- and open-shell systems utilizes a new automated toolchain for derivation, optimization, and evaluation of operator algebra in many-body electronic structure. We found that with a double-ζ basis set the 3CC correlation energies and their atomization energy contributions are almost always more accurate (with respect to the CCSDTQ reference) than the CCSDT model as well as the standard CCSD(T) model. The mean absolute errors in cc-pVDZ {3CC, CCSDT, and CCSD(T)} electronic (per valence electron) and atomization energies relative to the CCSDTQ reference for the HEAT data set [Tajti, A. . <i>J. Chem. Phys.</i> 2004, 121, 11599-11613.], were {24, 70, 122} μ<i>E</i>_h/<i>e</i> and {0.46, 2.00, 2.58} kJ/mol, respectively. The mean absolute errors in the complete-basis-set limit {3CC, CCSDT, and CCSD(T)} atomization energies relative to the HEAT model reference, were {0.52, 2.00, and 1.07} kJ/mol, The significant and systematic reduction of the error by the 3CC method and its lower cost than CCSDT suggests it as a viable candidate for post-CCSD(T) thermochemistry applications, as well as the preferred alternative to CCSDT in general.</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":"142542916","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":"Reactions of Diphenylamine with OH Radicals in the Environment: Theoretical Insights into the Mechanism, Kinetics, Temperature, and pH Effects.","authors":"Quan V Vo","doi":"10.1021/acs.jpcb.4c05366","DOIUrl":"10.1021/acs.jpcb.4c05366","url":null,"abstract":"<p><p>Diphenylamine (<b>DPL</b>) has been widely utilized in industrial chemicals, but its degradation by HO^• radicals in the environment has not been fully studied yet. The present study uses quantum chemical calculations to evaluate the reaction of <b>DPL</b> with HO^• radicals in atmospheric and aqueous environments. The results showed that, in the atmosphere, the diphenylamine reacted with the HO^• radical rapidly, with an overall rate constant of 9.24 × 10¹¹ to 1.34 × 10¹¹ M^-1 s^-1 and a lifetime of 0.17 to 1.55 h at 253-323 K. The calculated overall rate constant in water (<i>k</i>_overall = 1.95 × 10¹⁰ M^-1 s^-1, pH = 3-14) is in excellent agreement with the experimental value (<i>k</i>_overall = 1.00 × 10¹⁰-1.36 × 10¹⁰ M^-1 s^-1). The HO^• + <b>DPL</b> reaction in water could occur following the hydrogen transfer (15.4%), single electron transfer (41.6%), and radical adduct formation (41.7%) mechanisms, clarifying that addition products were not exclusive products. Nevertheless, variations in temperature and pH within aqueous environments had an impact on the mechanisms, kinetics, and degradation products of the reaction of <b>DPL</b> with HO^• radicals.</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":"142542925","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":"Minimizing Efficiency Roll-Off in Organic Emitters via Enhancing Radiative Process and Reducing Binding Energy: A Theory Insight.","authors":"Rui Liu, Yaqi Qi, Shaoqiao Zhao, Shulin Han, Yachen Cui, Yuzhi Song, Chuan-Kui Wang, Zongliang Li, Lei Cai","doi":"10.1021/acs.jpca.4c04754","DOIUrl":"10.1021/acs.jpca.4c04754","url":null,"abstract":"<p><p>Organic solid-state lasers have received increasing attention due to their great potential for realizing organic continuous-wave or electrically driven lasers. Moreover, they exhibit significant promise for optoelectronic devices due to their chemically tunable optoelectronic properties and cost-effective self-assembly traits. Recently, a great progress has been made in organic solid-state lasers via spatially separated charge injection and lasing. However, making directly electrically driven organic semiconductor lasers is very challenging. It is difficult because of a number of excitonic losses caused by the spin-forbidden nature as well as serious efficiency roll-off at a high current density. Here, a multifunction gain material, functioning both as a thermally activated delayed fluorescence (TADF) emitter with exceptional optical gain and as a source of phosphorescence, was theoretically investigated. The new molecule we designed exhibits a reduction of triplet accumulation through an effective exciton radiative process (5-fold boost in figure of merit) and significantly decreased exciton binding energy (dipole moment from 5.77 to 14.03 D), which benefit amplified spontaneous emission and lasing emission. Our work provides theoretical insights into organic solid-state lasers and may contribute to the development of new and efficient laser-gaining molecules.</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":"142556664","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 Δ<i>G</i> ∼ 0 to Identify the Real Active Site.","authors":"Xiang Huang, Xiangting Hu, Jiong Wang, Hu Xu","doi":"10.1021/acs.jpclett.4c02588","DOIUrl":"10.1021/acs.jpclett.4c02588","url":null,"abstract":"<p><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 Mo₂C as a prototype. We observe a contradictory scenario on Mo₂C MXene when using conventional thermodynamic descriptor Δ<i>G</i>_H* (hydrogen binding energy). Both competing surface phases that emerge close to the equilibrium potential meet the Δ<i>G</i>_H* ∼ 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 H₂ but are easily reduced to H₂O. 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>_H*. 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":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":"142556674","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":"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, Wei Huang","doi":"10.1021/acs.jpclett.4c02826","DOIUrl":"10.1021/acs.jpclett.4c02826","url":null,"abstract":"<p><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 × 10¹⁷ to 1.0 × 10¹⁹ cm^-3 and a transport layer mobility of >0.01 cm² V^-1 s^-1. 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":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":"142562605","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":"Electronic Structure of Diatomic Nickel Sulfide.","authors":"Nickolas A Joyner, João Gabriel Farias Romeu, Cole R Durkee, David A Dixon","doi":"10.1021/acs.jpca.4c06356","DOIUrl":"10.1021/acs.jpca.4c06356","url":null,"abstract":"<p><p>The nature of the Ni-S bond is investigated due to its role in the absorption of atmospheric Lewis acid gases such as SO₂ and SO₃ onto Ni surfaces. The vibrational frequency and electronic structure of NiS were predicted using CCSD(T), CASSCF, and internally contracted multireference configuration interaction (icMRCI) + Q. 43 density functional theory (DFT) functionals were benchmarked. CASSCF predicted the ground state of NiS to be the ⁵Δ state arising from the 3d⁸(³F)4s² (³F) and 3d⁹(²D)4s (³D) electronic configurations of Ni. When dynamical correlation effects are included at the icMRCI + Q level, the ground state of Ni-S is predicted to be ³Σ^- consistent with the experiment. The vibrational frequency of Ni-S is calculated to be 519.1 cm^-1 at the icMRCI + Q level, in reasonable agreement with the experimental value of 512.68 cm^-1. CCSD(T) predicts the frequency of Ni-S to be 543.2 cm^-1 when extrapolated to the complete basis set (CBS) limit. The Feller-Peterson-Dixon value based on the CCSD(T)/CBS extrapolation for the bond dissociation energy of NiS is 350.6 kJ/mol, within <4 kJ/mol of experiment. Of the 43 DFT functionals, BP86 and O3LYP predicted the vibrational frequency in closest agreement with the experiment. The applicability of DFT to such acid gas systems was further demonstrated by calculating the energy for displacement of NiO by SO to yield NiS and O₂. This displacement energy was calculated to be within experimental error for ∼50% of the DFT functionals, but large differences were also predicted for some functionals.</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":"142575442","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":"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, P C Stancil","doi":"10.1021/acs.jpclett.4c02865","DOIUrl":"10.1021/acs.jpclett.4c02865","url":null,"abstract":"<p><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":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":"142575466","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":"Increasing Cation Ion Symmetry Reduces Ionic Liquid Ordering in Thin Films.","authors":"Michael Blake Van Den Top, Andrew Horvath, Spyridon Koutsoukos, Frederik Philippi, Daniel Rauber, Tom Welton, Scott K Shaw","doi":"10.1021/acs.jpcb.4c04413","DOIUrl":"10.1021/acs.jpcb.4c04413","url":null,"abstract":"<p><p>Ionic liquids have been shown to form extended ordered structures near surfaces and in bulk. Identifying fundamental driving force(s) for this organization has been elusive. In this paper, we test a hypothesis that the ionic liquid asymmetry, inherent in many of the IL formulations to frustrate crystallization, is a significant contributor to the observed ordering. We have carried out measurements to track the ordering of ionic liquids composed of \"spherical\" cations, namely, tetraoctylphosphonium ([P8888]) and tetra(propoxymethyl)phosphonium [P(3O1)4] paired with tetracyanoborate anion [B(CN)4]. Analysis of the infrared signatures for films of these ionic liquids shows very little evidence of ordered structures. These liquids instead remain in a more isotropic environment even when confined to volumes of few micrometer dimensions.</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":"142580999","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":"Origins of Narrowband Emission in Nitrogen/Carbonyl Multiresonance Thermally Activated Delayed Fluorescence Emitters: Steric Locks and Vibrational Coupling Effects","authors":"Zhipeng Guo, Yanan Zhu, Aowei Zhou, Yang Zhao, Wanli Nie, Valentina Utochnikova, Hong Meng","doi":"10.1021/acs.jpclett.4c02423","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02423","url":null,"abstract":"The incorporation of <i>tert</i>-butyl groups and spiro-functionalization into C═O/N-embedded multiresonance thermally activated delayed fluorescence (MR-TADF) systems has yielded materials with superior narrowband emission and excellent color purity. To elucidate the mechanisms underlying the enhanced properties, we present a theoretical study of a series of fused nitrogen/carbonyl derivatives with narrower emission profiles. The key steric factors that contribute to narrowband emission were identified through energy decomposition analysis, induced by structural relaxation in states S₀ and S₁. Additionally, we achieved potential narrower-band and deep-blue emission by targeting the suppression of vibrational coupling effects. This work provides compelling evidence that a 1-<i>tert</i>-butyl substitution, acting as an end lock, offers minimal reorganization energy and optimal structural stability when combined with a fused lock. Furthermore, new compounds such as 1tBuCZQ and 1tBuDQAO have been identified as promising MR-TADF emitters, delivering ultranarrowband emission as high-quality organic light-emitting diodes.","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":"142610036","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":"Aminocarbonyl Fluorophores with a Strong Emissive Inverted Solvatochromism","authors":"Simone Morales, Matías Vidal, Fabián Martínez-Gómez, Raúl Mera-Adasme, Carolina Aliaga, Moisés Domínguez","doi":"10.1021/acs.jpclett.4c02457","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02457","url":null,"abstract":"Three aminocarbonyls were synthesized, and their emissive spectral behavior recorded at various solvent polarities showed marked inverted solvatofluorochromism. The emission energy inversion occurs at moderate solvent polarities and was found to be triggered by a change in the solute–solvent interaction responsible for the stabilization of the highly zwitterionic excited state of the dyes, from dipolarity to acidity.","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":"142610037","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}