The Journal of Physical Chemistry A最新文献

{"title":"A Review of Laboratory Studies on the Heterogeneous Chemistry of NO₂: Mechanisms and Uptake Kinetics.","authors":"Huiying Xuan, Chang Liu, Peng Zhang, Biwu Chu, Linlin Liang, Qingxin Ma, Hong He","doi":"10.1021/acs.jpca.4c07943","DOIUrl":"10.1021/acs.jpca.4c07943","url":null,"abstract":"<p><p>NO₂ is a significant primary atmospheric pollutant that plays a key role in atmospheric chemistry. It serves as a crucial precursor to photochemical smog, acid rain, and secondary particulate matter and is instrumental in determining the atmospheric oxidation capacity. In this review, we focus on the heterogeneous chemistry of NO₂, which has been demonstrated to significantly influence the sources and sinks of various nitrogen-containing species through field measurements and model simulations. We provide a comprehensive summary of laboratory studies investigating the reaction mechanisms and uptake kinetics of NO₂ in heterogeneous reactions. NO₂ can undergo disproportionation reactions on atmospheric particles. For instance, it may hydrolyze on wetted surfaces to form HONO and HNO₃, produce nitrate and NO on mineral dust, or generate nitrate and NOCl on sea salt. Additionally, NO₂ can be reduced to HONO on soot and Fe-bearing minerals or photocatalytically reduced to HONO and NO on photosensitive components. Furthermore, NO₂ can be photo-oxidized to nitrate or N₂O₅ on illuminated TiO₂. In addition, the synergistic effect of the heterogeneous reactions between NO₂ and SO₂ is discussed. The uptake coefficients of NO₂ on typical particles and the factors influencing these coefficients are also summarized. Finally, based on the current insufficient understanding of heterogeneous reactions of NO₂, we propose prospects for future research.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"815-835"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996312","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":"Projected Wave Function Extrapolation Scheme to Accelerate Plane-Wave Hybrid Functional-Based Born-Oppenheimer Molecular Dynamics Simulations.","authors":"Shizhe Jiao, Lingyun Wan, Jielan Li, Jun Gao, Xinming Qin, Wei Hu, Jinlong Yang","doi":"10.1021/acs.jpca.4c06241","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c06241","url":null,"abstract":"<p><p>Born-Oppenheimer molecular dynamics (BOMD) simulations are of great interest for the dynamic properties of molecular and solid systems. However, BOMD simulations necessitate not only an extensive period of dynamical evolution but also costly self-consistent-field (SCF) electronic structure calculations, especially for hybrid functional-based BOMD (H-BOMD) simulations within plane-wave basis sets. Here, we propose an improved always stable predictor-corrector (ASPC) method for the wave function extrapolation to accelerate the plane-wave H-BOMD simulations, named projected ASPC (PASPC), yielding a wave function closer to the actual solution space and efficiently reducing the number of SCF iterations at each MD step. We investigated the convergence properties of different extrapolation schemes for molecular and solid systems. Numerical results demonstrate that plane-wave H-BOMD simulations can be significantly faster than conventional cases by combining the accelerated algorithms with the PASPC method. The energy drift is also evaluated, showing that PASPC produces energy drift with smaller oscillations and can simulate a larger time step for systems containing heavy atoms, demonstrating the accuracy of the extrapolation schemes. Furthermore, H-BOMD simulations showcase more accurate power and infrared spectra of silicon dioxide and liquid water that are comparable to those of experimental measurements.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062512","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":"Resolving the Ambiguity of Thermal Reversion in a Nonconjugated Monocyclic Diene-Based Photoswitch for Rechargeable Solar Thermal Batteries.","authors":"Akanksha Ashok Sangolkar, Rama Krishna Kadiyam, Ravinder Pawar","doi":"10.1021/acs.jpca.4c04702","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c04702","url":null,"abstract":"<p><p>We report nonconjugated monocyclic dienes (nCMDs) as unique photoswitchable molecules that hold promise for harvesting substantial solar energy and storing it for extended durations. Herein, cyclohepta-1,4-diene <b>1a</b> and its N-heterocyclic analogue <b>2a</b> have been considered as prototypical models for investigating photoswitching behavior in nCMDs. Initially, the nonradiative deactivation pathway of nCMD from the low-lying excited state to the [2 + 2]-cycloadduct has been evaluated. This work resolves the ambiguity and rationalizes the kinetically preferred route for the regeneration of parent diene from a photoisomer that enables the thermo-reversible photoswitching cycle. Moreover, it sheds light on how the <i>syn</i>-<i>anti</i>-isomerism upon thermolysis facilitates the long-term storage of harvested solar energy. Extensive electronic structure analysis reveals that charge transfer from a lone pair on N restricts <i>syn</i>-<i>anti</i>-isomerism while promoting direct reversal of the photoproduct into diene and is highlighted as a pivotal factor for relatively short-term energy storage. The critical physical insights gained in this work are crucial for achieving efficient and sustainable solutions for solar thermal energy storage using novel photoswitches which can contribute to the global transition toward renewable energy sources.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062514","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":"Computational Explorations of Th⁴⁺ First Hydrolysis Reaction Constants: Insights from <i>Ab Initio</i> Molecular Dynamics and Density Functional Theory Calculations.","authors":"Yang He, Chang-Yi Tian, Shiru Wei, Zongchang Han, Han-Shi Hu, Jun Li","doi":"10.1021/acs.jpca.4c07469","DOIUrl":"10.1021/acs.jpca.4c07469","url":null,"abstract":"<p><p>The fundamental hydrolysis behavior of tetravalent actinide cations (An⁴⁺) with a high charge is crucial for understanding their solution chemistry, particularly in nuclear fuel reprocessing and environmental behavior. Using Th⁴⁺ as a reference of the An⁴⁺ series, this work employed both the periodic model and the cluster model to calculate the first hydrolysis reaction constant (p<i>K</i>_a1) of the Th⁴⁺ aqua ion and conducted a detailed evaluation of these approaches. In the periodic model, <i>ab initio</i> molecular dynamics (AIMD) simulations of Th⁴⁺ in the explicit solvation environment are conducted, using metadynamics and constrained molecular dynamics to calculate p<i>K</i>_a1 values. Metadynamics simulations with sufficient sampling yielded a value of 5.02, aligning with the experimental values (4.12-4.97). Moreover, AIMD results reveal further Grotthuss-type proton transfers and changes in the solvent structures, which are important for accurately modeling the hydrolysis process. In the cluster model, density functional theory calculations are performed on isolated hydrate clusters to obtain p<i>K</i>_a1 values, describing solvation effects through the cluster-continuum model. Based on insights from the periodic models, particularly regarding further proton transfer, the cluster model was modified and tested using different functionals and similar cations (La³⁺and Ac³⁺). The p<i>K</i>_a1 values obtained in the cluster model also show good agreement with the experimental values. The current computational approaches provide a comprehensive understanding of Th⁴⁺ hydrolysis and a reference framework for studying the hydrolysis of other lanthanide and actinide ions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1042-1050"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996321","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":"Photoelectron Imaging and Photodetachment Spectroscopy for the Cryogenically Cooled Cyanocyclopentadienide Anion.","authors":"Jisoo Kang, Edward I Brewer, Dao-Fu Yuan, Yue-Rou Zhang, Lai-Sheng Wang","doi":"10.1021/acs.jpca.4c07624","DOIUrl":"10.1021/acs.jpca.4c07624","url":null,"abstract":"<p><p>The cyano-cyclopentadiene molecule (CN-C₅H₅) has attracted significant interest since its detection in the interstellar medium, but the radical (CN-C₅H₄) and anionic (CN-C₅H₄^-) forms of cyano-cyclopentadiene have not been studied. The cyano-cyclopentadienyl radical (CN-Cp) has a strong dipole moment, rendering it an ideal system for vibrational and rotational spectroscopy. We report an investigation of the cryogenically cooled cyano-cyclopentadienide anion (CN-Cp^-) using high-resolution photoelectron imaging, photodetachment spectroscopy, and resonant photoelectron imaging. The electron affinity of the CN-Cp radical is measured accurately to be 2.7741 ± 0.0003 eV (22,375 ± 2 cm^-1). A low-lying excited state is observed for the CN-Cp neutral radical at 151 cm^-1 above the ground state. The overlap and vibronic coupling of the ground and low-lying electronic states give rise to complicated and congested photoelectron spectra. A dipole-bound state is observed for the CN-Cp^- anion with a binding energy of 94 cm^-1, along with 15 vibrational Feshbach resonances. Resonant photoelectron spectra via the vibrational resonances yield well-resolved spectra, allowing 26 vibronic levels to be identified for CN-Cp. The rich spectroscopic information will be valuable to compare with theoretical studies to unravel the vibronic coupling and nonadiabatic effects in the CN-Cp radical.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1060-1067"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996335","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":"Varying Projection Quality of Good Local Electric Field Gradients of Monochlorobenzaldehydes.","authors":"Robin Dohmen, Sean Arnold, Jessica Garrett, Beate Kempken, Beppo Hartwig, Benjamin Schröder, Pablo Pinacho, Melanie Schnell, Gordon G Brown, Daniel A Obenchain","doi":"10.1021/acs.jpca.4c04915","DOIUrl":"10.1021/acs.jpca.4c04915","url":null,"abstract":"<p><p>Rotational spectroscopy is an excellent tool for structure determination, which can provide additional insights into local electronic structure by investigating the hyperfine pattern due to nuclear quadrupole coupling. Jet-cooled molecules are good experimental benchmark targets for electronic structure calculations, as they are free of environmental effects. We report the rotational spectra of 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, and 4-chlorobenzaldehyde, including a complete experimental description of the nuclear quadrupole coupling constants, which were previously not experimentally determined. We identified two conformers for 3-chlorobenzaldehyde and one conformer each for 2-chlorobenzaldehyde and 4-chlorobenzaldehyde. Rigorous structure fitting of 4-chlorobenzaldehyde was performed to determine bond lengths for <i>r</i>₀, <i>r</i>_s, <i>r</i>_e^se, and <i>r</i>_<i>m</i>⁽¹⁾ structures. Comparing experimental nuclear quadrupole coupling constants to computational results showed agreement in the nuclear axis system, but the accuracy of the projection into the principal axis system decreases in near-oblate 2-chlorobenzaldehyde. The experimental angle Θ_az = 19.16° between the principal <i>a</i>-axis and nuclear <i>z</i>-axis is larger than predicted by multiple computational methods by ≥4°. It is attributed to the high sensitivity of 2-chlorobenzaldehyde to low-energy vibrational contributions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"860-873"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11789141/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996301","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":"Atom's Dynamics and Crystal Structure: An Ordinal Pattern Method.","authors":"Rafał Abram, Roman Nowak, Dariusz Chrobak","doi":"10.1021/acs.jpca.4c06151","DOIUrl":"10.1021/acs.jpca.4c06151","url":null,"abstract":"<p><p>The ubiquitous nature of thermal fluctuations poses a limitation on the identification of crystal structures. However, the trajectory of an atom carries a fingerprint of its surroundings. This rationalizes the search for a method that can determine the local atomic configuration via the analysis of the movement of an individual atom. Here, we report, while using molecular modeling, how a statistical analysis of a single-atom speed trajectory, represented by ordinal patterns, distinguishes between actual crystal structures. Using the Shannon entropy of ordinal patterns enabled discernment of the studied high-pressure silicon phases. Identification of the atoms occupying the 2(c) and 6(f) Wyckoff positions of the r8 crystal revealed an increase in the developed method's accuracy with trajectory length. The proposed concept of studying the structure of crystals offers new opportunities in solid-solid phase transformation studies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1136-1142"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11789147/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996317","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":"The Properties of the Low-Lying Electronic States and Avoided Crossings of the SbP Molecule: A Theoretical Investigation Includes Spin-Orbit Coupling.","authors":"Xin Zhou, Huagang Xiao, Tao Gao","doi":"10.1021/acs.jpca.4c06272","DOIUrl":"10.1021/acs.jpca.4c06272","url":null,"abstract":"<p><p>High-level multireference configuration interaction plus Davidson correction (MRCI + Q) calculation method was employed to determine the potential energy curves (PECs) of 10 Λ-S states, which come from the first and second dissociation channels of the SbP molecule, as well as 34 Ω states considering the spin-orbit coupling (SOC) effect. By solving the Schrödinger equation for nuclear motion, spectroscopic constants for the ground state X¹Σ⁺ and low-lying excited states were obtained and compared with experimental data. The excellent agreement indicates the reliability of our calculations. Additionally, the calculated spin-orbit (SO) matrix elements of the 1³Π and 1⁵Π states with other Λ-S states were analyzed, and the majority of the values in the Franck-Condon region exceed 200 cm^-1, indicating strong interactions between these states. What's more, the joint effects of spin-orbit coupling and avoided crossing were discussed in detail, leading to the complex potential energy curves and double-well phenomena observed in the Ω states. Taking forbidden transitions into account, transition dipole moments with the SOC effect are considered. The Franck-Condon factors, Einstein coefficients, and radiative lifetimes for the 1³Σ⁺₁ ↔ X¹Σ⁺₀₊ transition were obtained. Analysis indicates that direct laser cooling of SbP is inappropriate.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"946-954"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142976756","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":"Noncatalytic Reduction of Nitrogen Oxide and Soot Inhibition during Cocombustion with Biotar: The Molecular Dynamics Modeling Approach.","authors":"Shanhui Zhao, Yanquan Liu, Yinglei Wei, Jin Yan, Haiming Gu","doi":"10.1021/acs.jpca.4c07499","DOIUrl":"10.1021/acs.jpca.4c07499","url":null,"abstract":"<p><p>Cocombustion with biomass tar is a potential method for NO reduction during fossil fuel combustion. In this work, the molecular dynamic method based on the reactive force field was used to study the NO reduction by phenol, which is a typical tar model compound. Results indicate that phenol undergoes significant decomposition at 3000 K, resulting in the formation of small molecular fragments accompanied by the generation of large molecular, network-structured soot particles. At higher temperatures (3500 K), the morphology of the soot produced from phenol decomposition undergoes a certain degree of change. It evolves from a two-dimensional network structure to a three-dimensional particulate structure. Soot particles are significant products of the thermal decomposition process of phenol. NO acts as an oxidant during the phenol decomposition process, significantly inhibiting the formation of soot particles during this process. Phenol also promotes the reduction of NO. The corresponding NO reduction ratios of NO are 52%, 76%, and 89% for 1500, 2000, and 2500 K respectively. CO, H₂O, and N₂ were the three most important reaction products during phenol-NO interaction. HNO is an important intermediate during the reduction of NO by phenol. The combination of the H radical and NO is the main route for HNO. It can be seen that HNO is quickly produced at the initial stage. The calculated activated energies for NO reduction and phenol oxidation are 30.47 and 50.85 kJ/mol, respectively.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1125-1135"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996333","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":"Ab Initio Rotational and Vibrational Spectroscopy of C₃H₅ Radicals at the Coupled Cluster Level.","authors":"Kyle N Crabtree, Adam A Culick, Chisom A Dim, Izzy A Muise, J H Westerfield, Sophia E Worthington-Kirsch","doi":"10.1021/acs.jpca.4c05478","DOIUrl":"10.1021/acs.jpca.4c05478","url":null,"abstract":"<p><p>Combustion and pyrolysis processes of allene and propyne are known to involve radicals with the structural formula C₃H₅, the most stable of which is the classic resonance-stabilized allyl radical. In addition to allyl, four other isomers of C₃H₅ are possible: the propene derivatives <i>Z</i>-1-propenyl, <i>E</i>-1-propenyl, and 2-propenyl, as well as the cyclopropane derivative cyclopropyl. Among these 5 species, the allyl radical has been extensively studied both theoretically and spectroscopically; however, little is known about the spectroscopy of the cyclopropyl radical, and virtually no experimental spectroscopic data are available for the remaining three. Here, we carry out an ab initio investigation of the C₃H₅ radicals at the coupled cluster level of theory with a focus on computing the spectroscopic parameters relevant for pure rotational and rotationally resolved vibrational spectroscopy. The rotational constants, dipole moments, spin-spin tensors, and Fermi contact parameters are evaluated at the CCSD(T)/cc-pwCVQZ level of theory, while vibrational properties such as vibration-rotation interaction parameters and centrifugal distortion constants are calculated at the frozen-core CCSD(T)/ANO1 level. Vibrational analysis was carried out using second-order vibrational perturbation theory with an explicit treatment of resonances. Finally, the inversion tunneling potential in cyclopropyl as well as the methyl internal rotation potentials in the 1- and 2-propenyl isomers are computed and relevant spectroscopic parameters for modeling their resultant tunneling splittings are derived. Results from the calculations compare favorably with the extensive body of spectroscopic literature on the allyl radical, giving confidence that the computed parameters for the remaining isomers will be useful for guiding the interpretation of future high-resolution experimental spectroscopy of these radicals.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"909-923"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11789146/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996314","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}