The Journal of Physical Chemistry A最新文献_第2页

Tuning Vibrational Lifetimes by Chemical Substitution and Impact on Plasmon-Assisted Catalysis.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-17 DOI: 10.1021/acs.jpca.4c08207

Pathick Halder Shaon, Humanath Poudel, David M Leitner

{"title":"Tuning Vibrational Lifetimes by Chemical Substitution and Impact on Plasmon-Assisted Catalysis.","authors":"Pathick Halder Shaon, Humanath Poudel, David M Leitner","doi":"10.1021/acs.jpca.4c08207","DOIUrl":"10.1021/acs.jpca.4c08207","url":null,"abstract":"Recent experiments indicate that the NO stretch of 4-nitrobenzenethiol (NBT) attached to gold can be selectively excited via plasmonic excitation, catalyzing the decomposition of NBT. However, the effectiveness of catalysis is limited by intramolecular vibrational redistribution, which depletes the population of the excited NO stretch in a few picoseconds. In this study, vibrational lifetimes of the NO stretch are computed quantum mechanically for 20 substituted NBTs, including 10 chemical groups in the meta and ortho positions, attached to plasmonic nanoparticles. Variation in the lifetime of the NO stretch with chemical substitution arises from the tuning of resonances as well as systematic changes in values of anharmonic constants. The lifetime of the NO stretch of NBT depends largely on resonances involving three other modes. Upon substitution, one of those modes shifts far enough in frequency that it no longer affects the NO stretch lifetime. For substituents in the ortho position, new resonances appear that can shorten the lifetime, but most are detuned, and the coupling is weaker for the same substituents in the meta position. The impact of the longer NO stretch lifetimes found, particularly for substituents in the meta position, on enhancing the population of the NO stretch and catalysis is discussed.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2006-2015"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439398","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}

引用次数: 0

Overview on Building Blocks and Applications of Efficient and Robust Extended Tight Binding.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 DOI: 10.1021/acs.jpca.4c08263

Abylay Katbashev, Marcel Stahn, Thomas Rose, Vahideh Alizadeh, Marvin Friede, Christoph Plett, Pit Steinbach, Sebastian Ehlert

{"title":"Overview on Building Blocks and Applications of Efficient and Robust Extended Tight Binding.","authors":"Abylay Katbashev, Marcel Stahn, Thomas Rose, Vahideh Alizadeh, Marvin Friede, Christoph Plett, Pit Steinbach, Sebastian Ehlert","doi":"10.1021/acs.jpca.4c08263","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08263","url":null,"abstract":"The extended tight binding (xTB) family of methods opened many new possibilities in the field of computational chemistry. Within just 5 years, the GFN2-xTB parametrization for all elements up to Z = 86 enabled more than a thousand applications, which were previously not feasible with other electronic structure methods. The xTB methods provide a robust and efficient way to apply quantum mechanics-based approaches for obtaining molecular geometries, computing free energy corrections or describing noncovalent interactions and found applicability for many more targets. A crucial contribution to the success of the xTB methods is the availability within many simulation packages and frameworks, supported by the open source development of its program library and packages. We present a comprehensive summary of the applications and capabilities of xTB methods in different fields of chemistry. Moreover, we consider the main software packages for xTB calculations, covering their current ecosystem, novel features, and usage by the scientific community.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514123","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}

引用次数: 0

Electronic Structure and Spectroscopy of CuBe.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-13 DOI: 10.1021/acs.jpca.4c08565

Arianna Rodriguez, Sophia Vadachkoria, Francesco A Evangelista, Michael C Heaven

引用次数: 0

Influence of Water on the NO₃ + HO₂ Reaction.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-17 DOI: 10.1021/acs.jpca.4c08696

Philips Kumar Rai, Pradeep Kumar

引用次数: 0

Interplays between Functional Groups and Substitution Sites Modulate the Photophysics of the Bithiophenes.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-17 DOI: 10.1021/acs.jpca.4c08513

Haijun Fu, Zhendong Li, Yanying Zhao, Jingbai Li

{"title":"Interplays between Functional Groups and Substitution Sites Modulate the Photophysics of the Bithiophenes.","authors":"Haijun Fu, Zhendong Li, Yanying Zhao, Jingbai Li","doi":"10.1021/acs.jpca.4c08513","DOIUrl":"10.1021/acs.jpca.4c08513","url":null,"abstract":"Bithiophene has an electron-rich conjugated ring, enabling highly tunable photophysical properties for the design of novel organic light-emitting materials. Extensive research was focused on the functionalization of α-site-connected bithiophene, while recent work reported the synthesis of β-bithiophene, substantially enlarging the chemical space for bithiophene design. However, the design rule for modulating the physical properties of β-bithiophene has remained unexplored. We performed comprehensive quantum chemical calculations to investigate how functional groups and substituent sites control the absorption and emission wavelengths of β-bithiophene. Our results show that the functional groups lead to red-shifts of the wavelengths by extending the electron delocalization, while the substitution sites have fewer effects on the wavelengths. The absorption and emission calculation for trithiophene and tetrathiophene suggest that the photophysical properties of thiophene polymer are controlled by the short thiophene chains, underscoring the significance of the rational design of β-bithiophene derivatives.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2033-2040"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439395","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}

引用次数: 0

Kinetics of the Reaction Between the Criegee Intermediate CH₂OO and NO₂: Experimental Measurements and Comparison with Theory.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-12 DOI: 10.1021/acs.jpca.4c08203

Rachel E Lade, Kate A Livesey, Luc Vereecken, Robin J Shannon, Mark A Blitz, Paul W Seakins, Daniel Stone

{"title":"Kinetics of the Reaction Between the Criegee Intermediate CH2OO and NO2: Experimental Measurements and Comparison with Theory.","authors":"Rachel E Lade, Kate A Livesey, Luc Vereecken, Robin J Shannon, Mark A Blitz, Paul W Seakins, Daniel Stone","doi":"10.1021/acs.jpca.4c08203","DOIUrl":"10.1021/acs.jpca.4c08203","url":null,"abstract":"Kinetics of the gas phase reaction between the stabilized Criegee intermediate formaldehyde oxide (CH2OO) and nitrogen dioxide (NO2) have been measured using laser flash photolysis of CH2I2/O2/N2/NO2 mixtures coupled with time-resolved broadband ultraviolet absorption spectroscopy. Experiments were performed in N2 under pseudo-first-order conditions at temperatures between 242 and 353 K and pressures in the range 25 to 300 Torr. The kinetics of CH2OO + NO2 are independent of pressure, with a mean rate coefficient of k1 = (1.24 ± 0.22) × 10-12 cm3 s-1 at 298 K, where the uncertainty represents a combination of the 1σ statistical error and the systematic errors resulting from uncertainties in gas flow rates and in the concentration of NO2. Measurements indicate upper limits of <5% for production of NO3 and <5% for production of NO, and further studies of product yields are warranted. In contrast to expectations from theory, the kinetics of CH2OO + NO2 display a negative temperature dependence that can be described by k1 = (1.07 ± 0.02) × 10-12 × (T/298)-(2.9±0.2) cm3 s-1. Analysis using the Master Equation Solver for Multi-Energy well Reactions is able to reproduce a negative temperature dependence for the reaction if significant changes to barrier heights are made, but the overall agreement between the experiment and theory remains poor. This work highlights the challenges associated with calculations for systems with significant multi-reference character.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2058-2066"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404918","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}

引用次数: 0

Experimental Confirmation of van der Waals-Enhanced Growth of Sulfuric Acid/Water Nanoparticles.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-18 DOI: 10.1021/acs.jpca.4c07693

David R Hanson, Amanda S Case, Karl Froyd

{"title":"Experimental Confirmation of van der Waals-Enhanced Growth of Sulfuric Acid/Water Nanoparticles.","authors":"David R Hanson, Amanda S Case, Karl Froyd","doi":"10.1021/acs.jpca.4c07693","DOIUrl":"10.1021/acs.jpca.4c07693","url":null,"abstract":"Since the size of an atmospheric particle determines many of its effects, we conducted experiments to better understand their rate of growth. Seed particles composed of sulfuric acid and water were exposed to photolytically generated H2SO4 molecules and their change in size was monitored with a mobility particle system. H2SO4 production rates were held steady while the seed particle diameter was varied from 3 to 25 nm to explore how growth is affected by size. The growth rate of 25 nm diameter particles was about 50% less than that for 3 nm diameter particles. Gas-kinetic hard-sphere growth rates decline only 18% over this size range, but a decrease of 35-to-50% in growth over this range is expected according to theories that include the effects of a van der Waals interaction between gaseous H2SO4 and the small particles. The size-dependence of the measured growth rates, which does not require knowledge of the H2SO4 gas concentration, suggests that the attractive force between hydrated H2SO4 and small sulfuric acid particles leads to a significant enhancement of the collision rate; this force depends strongly on particle size below 10 nm in diameter. Recent calculations based on a central field approximation for the van der Waals interaction are consistent with the measurements, although empirical enhancement factors better explain the data for some conditions. Nucleation experiments were also performed with H2SO4 detection, and simulations of these nucleation experiments required similar van der Waals enhancements to secure agreement between measured H2SO4 vapor and the size of the nucleated particles.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2049-2057"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439393","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}

引用次数: 0

Dynamics Study of the CaC (X³∑^-) + C(³P_g) → Ca+C₂ (∑v) Reaction: Based on a Full-Dimensional Neural Network Potential Energy Surface of CaC₂.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-14 DOI: 10.1021/acs.jpca.4c08437

Guosen Wang, Xia Huang, Changmin Guo, Hong Zhang, Chuanyu Zhang, Xinlu Cheng

{"title":"Dynamics Study of the CaC (X3∑-) + C(3Pg) → Ca+C2 (∑v) Reaction: Based on a Full-Dimensional Neural Network Potential Energy Surface of CaC2.","authors":"Guosen Wang, Xia Huang, Changmin Guo, Hong Zhang, Chuanyu Zhang, Xinlu Cheng","doi":"10.1021/acs.jpca.4c08437","DOIUrl":"10.1021/acs.jpca.4c08437","url":null,"abstract":"The CaC2 molecule, as an interstellar species that has already been detected, has attracted significant attention. To date, studies on the potential energy surface (PES) and the reaction dynamics of CaC2 are largely lacking. In this work, ab initio energy values were obtained for 3877 configurations using the icMRCI+Q method, and these energies were subsequently fitted using a neural network approach. During parameter optimization, the trust region framework (TRF) method, which has superior performance compared to the previously used Levenberg-Marquardt (LM) method, was used. The root-mean-squared error (RMSE) for both the training and testing sets meets the requirement for chemical accuracy (error less than 1 kcal/mol). Using the neural network PES, we identified one stable structure and two metastable structures for the ground state (X̃1A') of CaC2. The stable structure is T-shaped, while the two metastable structures are linear. The potential well depths of the stable structure and the two metastable structures are -10.98, -9.75, and -4.70 eV, respectively. Based on the obtained full-dimensional neural network PES, we investigated the CaC(X3Σ-) + C(3Pg) → Ca + C2 (Σv) reaction dynamics under different initial conditions. Under the condition that all other parameters remain unchanged, the reaction cross section and rate constant were found to be largest when the initial condition was v = 0 and j = 0. These findings indicate that the reaction rate is fastest when the CaC molecule is in its ground state.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"2024-2032"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412410","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}

引用次数: 0

Photoswitching Molecules Functionalized with Optical Cycling Centers Provide a Novel Platform for Studying Chemical Transformations in Ultracold Molecules. 光循环中心功能化的光开关分子为研究超冷分子的化学转化提供了一个新的平台。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2024-12-19 DOI: 10.1021/acs.jpca.4c06320

Paweł Wójcik, Taras Khvorost, Guanming Lao, Guo-Zhu Zhu, Antonio Macias, Justin R Caram, Wesley C Campbell, Miguel A García-Garibay, Eric R Hudson, Anastassia N Alexandrova, Anna I Krylov

{"title":"Photoswitching Molecules Functionalized with Optical Cycling Centers Provide a Novel Platform for Studying Chemical Transformations in Ultracold Molecules.","authors":"Paweł Wójcik, Taras Khvorost, Guanming Lao, Guo-Zhu Zhu, Antonio Macias, Justin R Caram, Wesley C Campbell, Miguel A García-Garibay, Eric R Hudson, Anastassia N Alexandrova, Anna I Krylov","doi":"10.1021/acs.jpca.4c06320","DOIUrl":"10.1021/acs.jpca.4c06320","url":null,"abstract":"A novel molecular structure that bridges the fields of molecular optical cycling and molecular photoswitching is presented. It is based on a photoswitching molecule azobenzene functionalized with one and two CaO- groups, which can act as optical cycling centers (OCCs). This paper characterizes the electronic structure of the resulting model systems, focusing on three questions: (1) how the electronic states of the photoswitch are impacted by a functionalization with an OCC; (2) how the states of the OCC are impacted by the scaffold of the photoswitch; and (3) whether the OCC can serve as a spectroscopic probe of isomerization. The experimental feasibility of the proposed design and the advantages that organic synthesis can offer in the further functionalization of this molecular scaffold are also discussed. This work brings into the field of molecular optical cycling a new dimension of chemical complexity intrinsic to only polyatomic molecules.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1929-1940"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142862538","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}

引用次数: 0

Vibrational Energy Transfer upon the Collision of NO with VO₂ Thin Films across the Insulator-to-Metal Transition.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-02-27 Epub Date: 2025-02-17 DOI: 10.1021/acs.jpca.4c08096

Artur Meling, Tony Yamin, Alexander Kandratsenka, Amos Sharoni, Tim Schäfer, Igor Rahinov

{"title":"Vibrational Energy Transfer upon the Collision of NO with VO2 Thin Films across the Insulator-to-Metal Transition.","authors":"Artur Meling, Tony Yamin, Alexander Kandratsenka, Amos Sharoni, Tim Schäfer, Igor Rahinov","doi":"10.1021/acs.jpca.4c08096","DOIUrl":"10.1021/acs.jpca.4c08096","url":null,"abstract":"The mechanism and consequently the magnitude of vibrational relaxation of molecules on surfaces differ significantly between insulators and metals, making the vibrational energy transfer at the NO/metal versus the NO/insulator interface a canonical example in the field. We report the influence of the surface temperature, the initial vibrational state, and the incident translational energy on the vibrational relaxation probability of vibrationally excited NO(vI = 3 and vI = 11) undergoing a direct scattering from thin films of vanadium dioxide (VO2) across the Mott transition at 68 °C. At that temperature, thin-film VO2 transforms from the insulating to the metallic phase, exhibiting ∼4 orders of magnitude drop in resistivity. As VO2 undergoes the Mott transition, at T > 68 °C, we observe a surprisingly small, yet measurable enhancement in the relaxation probability of NO(vI = 3 and vI = 11) due to the metallic phase of VO2. The magnitudes of vibrational relaxation for NO(vI = 3)/VO2 and NO(vI = 11)/VO2 are ∼2 and ∼20%, respectively─considerably lower than expected, based on the S-shaped dependence of vibrational relaxation probability on the asymptotic affinity level, observed for diatomic molecules on coinage metal surfaces. By analyzing the distinct dynamic features of NO scattering, including the dependence of vibrational relaxation on the initial vibrational state and on the incidence energy, as well as the relationship between rotational excitation and vibrational inelasticity, we explain the low magnitude of vibrational relaxation of NO on VO2 using the electron transfer model.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1993-2005"},"PeriodicalIF":2.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439399","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}

引用次数: 0