The Journal of Physical Chemistry A最新文献

{"title":"The Noncovalent Interaction in Dinuclear Bridged Gold(I) Complexes: A Theoretical Study.","authors":"Dina Lara, Néstor Gutiérrez-Sánchez, Sebastián Miranda-Rojas, Fernando Mendizabal","doi":"10.1021/acs.jpca.4c06026","DOIUrl":"10.1021/acs.jpca.4c06026","url":null,"abstract":"<p><p>We present a study of the cooperative nature of the forces dominating the interaction between gold atoms and aryl-aryl stacking. For this purpose, we modeled a series of complexes of the type dpm(AuR)₂ (dpm= bis(phoshino)methane; R = -C₆H₅, -C₆F₅, -C₆Cl₅, and -Cl). The models were calculated at the MP2, CCSD(T), and DFT-D3(BJ) (PBE and TPSS) levels of theory. The results show Au-Au and aryl-aryl stacking distances associated with noncovalent interactions. Also, the Wiberg indices, NBO, NCI, and QTAIM analyses exposed a low-density character between the gold atoms and aryl-aryl stacking, revealing that this contribution explains the stability of the complexes via dispersive interactions. Finally, the absorption spectra obtained are comparable with the experimental ones, and the orbitals obtained demonstrate that after the transitions, the orbitals are delocalized between the gold atoms and the vertex atoms of the molecules.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"66-75"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845317","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":"Potential Energy Curves of Hydrogen Halides HX(F, Cl, Br) with the <i>i</i>-DMFT Method.","authors":"Di Liu, Marinela Irimia, Jian Wang, Bing Yan","doi":"10.1021/acs.jpca.4c08229","DOIUrl":"10.1021/acs.jpca.4c08229","url":null,"abstract":"<p><p>The information entropy based on the occupation numbers has been found to play a central role in a description of electron correlation within the density-matrix functional theory [<i>i</i>-DMFT, see <i>Phys. Rev. Lett.</i> <b>2022</b>, 128, 013001]. In this article, the <i>i</i>-DMFT method is applied to predict potential energy curves, equilibrium bond lengths, and harmonic vibrational frequencies for the hydrogen halides: HF, HCl, and HBr. The results are compared with other theoretical calculations and experimental spectroscopic data.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"415-422"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875491","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":"d-p Hybridization Induced Open-Shell Planar Four-Membered Transition Metal Carbide Clusters with Double Möbius Aromaticity.","authors":"Jun Li, Yun-Ting Bu, Ao-Hua Wang, Jing Chen, Shi-Bo Cheng","doi":"10.1021/acs.jpca.4c05405","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c05405","url":null,"abstract":"<p><p>Aromaticity is one of the most classical concepts in the field of modern chemistry and has been employed to explain and design substances with special stability. Although the knowledge about Hückel's and Baird's rules has been well established, the understanding of Möbius aromaticity remains extremely limited. In this letter, by employing density functional theory (DFT) calculations, we demonstrated that the four-membered VIB transition metal (TM) carbide clusters possess a highly stable open-shell planar tetrameric structure and exhibit double Möbius aromaticity, which was evidenced by analyzing multiple aromaticity criteria, including the electronic, magnetic, and energetic indicators. Each cluster was characterized by four delocalized π electrons and four delocalized σ electrons, forming a novel class exhibiting double Möbius aromaticity. Intriguingly, the unexpected stability of these open-shell clusters was suggested to arise from the hybridization of d-p atomic orbitals, as revealed by analysis of the composition of delocalized orbitals. Our findings highlight the significance of hybridization between the d orbitals of transition metals and the p orbitals of main group elements in the creation of dual Möbius aromatic species, which offers new avenues for the design of single-molecule magnetic inorganic materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 1","pages":"28-35"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941477","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":"Balance of Unimolecular and Bimolecular Pathways Control the Temperature-Dependent Kinetics of Ozonolysis in Aerosols.","authors":"Ryan S Reynolds, Kevin R Wilson","doi":"10.1021/acs.jpca.4c06885","DOIUrl":"10.1021/acs.jpca.4c06885","url":null,"abstract":"<p><p>To better understand the key kinetic mechanisms controlling heterogeneous oxidation in organic aerosols, submicron particles composed of an alkene and a saturated carboxylic acid are exposed to ozone in a variable-temperature flow tube reactor. Effective uptake coefficients (γ_eff) are obtained from the multiphase reaction kinetics, which are quantified by Vacuum Ultraviolet Photoionization Aerosol Mass Spectrometry. For aerosols composed of only of alkenes, γ_eff doubles (from 6 × 10^-4 to 1.2 × 10^-3) when the temperature is decreased from 293 to 263 K. Alternatively, for an alkene particle doped with a carboxylic acid, an efficient scavenger of stabilized Criegee Intermediates (sCI), γ_eff is observed to be weakly temperature dependent. A kinetic model, benchmarked to literature data, explains these results as arising from the temperature dependent competition between unimolecular pathways of sCI that promote radical chain cycling and those bimolecular pathways that form stable chain termination products (i.e., α-acyloxyalkyl hydroperoxides). The implication of these results for the kinetics of aerosol aging at low temperatures is discussed.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"232-243"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870578","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":"A Quantum Chemistry Insight into the Potential Role of the Singlet Oxygen-Acetone System as a Source for Production of Stable Secondary Organic Aerosols through a Multiwell Multipath Reaction.","authors":"Hamed Douroudgari, Sara Asgari, Morteza Vahedpour","doi":"10.1021/acs.jpca.4c05991","DOIUrl":"10.1021/acs.jpca.4c05991","url":null,"abstract":"<p><p>The high abundance of acetone ((CH₃)₂C═O), which makes it a good candidate for oxygenated molecules, and the high reactivity of oxygen atoms in the first excited state O(¹D) are two well-known facts in the chemistry of the atmosphere. In this research, we prove that the singlet oxygen and acetone system is capable of proceeding through multiwell multipath reactions, leading to the production of several organic aerosols. Hence, the nature of species released by the (CH₃)₂C═O + O(¹D) reaction to air can be clarified by profound attention to the possible routes. To verify this, the singlet potential energy surface (PES) of the acetone + O(¹D) reaction is investigated by using various validated quantum chemistry approaches, especially the high-cost BD(TQ) method. By the carefully chosen theoretical methods, we forecast all possible multistep routes with high accuracy for the production of possible adducts in reliable conditions. Also, we use the kinetic results of the well-proven theories (TST and RRKM) to show the importance and atmospheric relevance of the simulated reactions. So, the rate constants of the (CH₃)₂C═O + O(¹D) reaction channels are computed at a large temperature range employing precise energetics and partition functions to show which products have a high percentage of yield. Moreover, the competitive canonical unified statistical (CCUS) model is utilized to show whether pressure influences the products generated by barrierless reactions. In addition, the thermodynamic functions of stationary points (at 298 K) and the rate constants of the found reaction routes demonstrate that the reaction adducts are very stable, so the reverse reactions have less importance compared to the forward reactions. In summary, this study illustrates how designed reaction routes could play a vital role in secondary aerosol formation in the atmosphere.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"207-221"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890695","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":"Spectroscopy and Dynamics of the Dipole-Bound States of <i>ortho</i>-, <i>meta</i>-, and <i>para</i>-Methylphenolate Anions.","authors":"Jinwoo Kim, Junggil Kim, Sang Kyu Kim","doi":"10.1021/acs.jpca.4c07507","DOIUrl":"10.1021/acs.jpca.4c07507","url":null,"abstract":"<p><p>A photodetachment and photoelectron spectroscopic study by employing a cryogenically cooled ion trap combined with a velocity-map imaging setup has been carried out to unravel the vibrational structures and autodetachment dynamics of the dipole-bound states (DBSs) of <i>o</i>-, <i>m</i>-, and <i>p</i>-methylphenolate anions (<i>o</i>-, <i>m</i>-, and <i>p</i>-CH₃PhO^-). The electron binding energy of the DBS increases monotonically with the increase of the neutral dipole moment to give respective values of 66 ± 15, 123 ± 18, or 154 ± 14 cm^-1 for the <i>o</i>-, <i>m</i>-, or <i>p</i>-isomer. The different electron-donating effects of the methyl moieties in the three geometrically different isomers seem to be reflected in the experiment. Mode-specific DBS dynamics of the <i>o</i>-, <i>m</i>-, and <i>p</i>-CH₃PhO^- complexes have been interrogated by using picosecond time-resolved photoelectron velocity-map imaging spectroscopy. Autodetachment lifetimes of the DBS vibrational Feshbach resonances have been measured and discussed quantitatively using Fermi's golden rule, especially in comparison with those of the phenoxide anion to get insights into the methyl substitution effect on the electron binding dynamics of the metastable DBS.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"174-179"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890552","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":"General Spin-Restricted Open-Shell Configuration Interaction Approach: Application to Metal K-Edge X-ray Absorption Spectra of Ferro- and Antiferromagnetically Coupled Dimers.","authors":"Tiago Leyser da Costa Gouveia, Dimitrios Maganas, Frank Neese","doi":"10.1021/acs.jpca.4c05228","DOIUrl":"10.1021/acs.jpca.4c05228","url":null,"abstract":"<p><p>In this work, we present a generalized implementation of the previously developed restricted open-shell configuration interaction singles (ROCIS) family of methods. The new method allows us to treat high-spin (HS) ferro- as well as antiferromagnetically (AF) coupled systems while retaining the total spin as a good quantum number. To achieve this important and nontrivial goal, we employ the machinery of the iterative configuration expansion (ICE) method, which is able to tackle general configuration interaction (CI) problems on the basis of spin-adapted configuration state functions (CSFs). While ICE is designed to work in restricted orbital spaces, the new general-spin ROCIS (GS-ROCIS) method is designed to be applicable to larger molecules by employing a prototyping strategy. This new method can be applied to closed-shell, high-spin open-shell, as well as antiferromagnetic reference CSFs. In addition, GS-ROCIS can be combined with the pair natural orbital (PNO) machinery in the form of the PNO-GS-ROCIS method. With this extension, one can drastically reduce the required virtual space in the vicinity of the involved core orbitals, leading to computational savings of several orders of magnitude with negligible (<1%) loss in accuracy. To demonstrate the use of the new methodology, the metal K pre-edge X-ray absorption excitation problem of an antiferromagnetically coupled copper model dimer was investigated. By first analyzing a model copper dimer, it is shown that even for the minimum core excitation problem that involves the two antiferromagnetically coupled singly occupied orbitals and one virtual orbital, the resulting GS-ROCIS and broken-symmetry configuration interaction singles (BS-CIS) spectra may differ in terms of the number, energy position, and relative intensity of the computed bands. Furthermore, the methodology was validated to perform equally well in computing the K-edge spectra of antiferromagnetic nickel oxide dimers and mixed-valence cobalt oxide trimers. Collectively, the present development represents an important methodological advance in the application of theoretical X-ray spectroscopy.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"330-345"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11726630/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833159","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":"Infrared Spectroscopy of Isocyano-Polycyclic Aromatic Hydrocarbons: The NC Stretch.","authors":"Vincent J Esposito, Ryan C Fortenberry, Christiaan Boersma, Louis J Allamandola","doi":"10.1021/acs.jpca.4c07416","DOIUrl":"10.1021/acs.jpca.4c07416","url":null,"abstract":"<p><p>Anharmonic computations reveal an intense, narrow (20 cm^-1, 0.043 μm) absorption feature at approximately 2160 cm^-1 (4.63 μm) in the vibrational spectra of 14 prototypical singly isocyano-substituted polycyclic aromatic hydrocarbons (NC-PAHs) attributed to the NC stretching mode. The intrinsically bright NC stretching mode and strong anharmonic coupling to other states in this region of the spectrum, along with the presence of multiple isomers of each NC-PAH, creates a complex, intense band for each molecule alone, and for the group of molecules as a whole. The NC stretching feature is shifted approximately 130 cm^-1 to lower frequency compared to the CN stretching feature of cyano-substituted PAHs. This shift is due to the weaker NC bond as a result of the zwitterionic character of the NC-PAHs. Advanced resonance polyad matrices are utilized in the second order vibrational perturbation treatment, providing in-depth understanding of the spectroscopic characteristics of each vibrational transition. These detailed spectroscopic data are provided for use in analysis of future laboratory experiments and the search for NC-PAHs in astronomical observations. Such data will be vital to the continued benchmarking of computational methodologies for use in exotic, substituted PAHs that have never been studied before.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"244-252"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875490","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":"Vibronic Structure of the UV/Visible Absorption Spectra of Phenol and Phenolate: A Hybrid Density Functional Theory─Doktorov's Quantum Algorithm Approach.","authors":"Renato Olarte Hernandez, Armand Soldera, Benoît Champagne","doi":"10.1021/acs.jpca.4c06960","DOIUrl":"10.1021/acs.jpca.4c06960","url":null,"abstract":"<p><p>The Doktorov's quantum algorithm has been enacted in combination with time-dependent density functional theory (TD-DFT) to simulate the vibronic structure of the UV/visible absorption spectra of the phenol and phenolate molecules. On the one hand, DFT and TD-DFT are employed with classical algorithms to calculate the ground and excited-state electronic structures as well as their vibrational frequencies and normal modes, whereas, on the other hand, quantum algorithms are employed for evaluating the vibrational transition intensities. In comparison to a previous study, <i>J. Phys. Chem. A</i> <b>2024</b>, 128, 4369-4377, which demonstrated Doktorov's quantum algorithm as a proof of concept to predict the vibronic structure of ionization spectra, it is applied here to medium-size molecules with more than 30 vibrational normal modes, without accounting for Duschinsky rotations due to software limitations. This application to simulate the vibronic structures of the spectra of phenol and phenolate also enables assessing the impact of the differences in vibrational frequencies between the ground and excited electronic states.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"396-406"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884818","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":"Univariate Prediction of Hammett Parameters and Select Relative Reaction Rates Using Loewdin Atomic Charges.","authors":"Gautam D Stroscio, Nir Goldman","doi":"10.1021/acs.jpca.4c05805","DOIUrl":"10.1021/acs.jpca.4c05805","url":null,"abstract":"<p><p>Loewdin charges from density functional theory calculations were used here to obtain general, univariate linear correlations for the prediction of experimental Hammett parameters and relative reaction rates. While previous studies have established that Hirshfeld and CM5 charges perform strongly as univariate predictors, the near-ubiquitous Loewdin charges have not yet been evaluated. To this end, we assess the predictive capability of Loewdin charges for three chemical systems. First, we show that Loewdin charges outperform Hirshfeld and CM5 charges for Hammett parameter prediction. Second, we see that Loewdin charges generally perform comparably to Hirshfeld charges for predicting the relative rates of olefin cleavage by photoexcited nitroarenes. The single case of poor correlation, between relative rates and the Loewdin charges on nitrogen sites, is ameliorated when considering the net charge on the NO₂ group. Third, we show that Loewdin, Hirshfeld, and CM5 charges all perform very well for generating correlations for relative reaction rates for C-H activation of 9-(4-X-phenyl)-9<i>H</i>-fluorene substrates by a transition metal catalyst. The equations generated throughout the study enable the prediction of Hammett parameters and relative reaction rates. These tools can accelerate synthetic and experimental studies by enabling the in silico prediction of uncharacterized chemical properties.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"356-366"},"PeriodicalIF":2.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890554","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}