The Journal of Physical Chemistry A最新文献

Potential Energy Curves of Hydrogen Halides HX(F, Cl, Br) with the i-DMFT Method.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-23 DOI: 10.1021/acs.jpca.4c08229

Di Liu, Marinela Irimia, Jian Wang, Bing Yan

引用次数: 0

Infrared Spectroscopy of Isocyano-Polycyclic Aromatic Hydrocarbons: The NC Stretch.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-23 DOI: 10.1021/acs.jpca.4c07416

Vincent J Esposito, Ryan C Fortenberry, Christiaan Boersma, Louis J Allamandola

{"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":"https://doi.org/10.1021/acs.jpca.4c07416","url":null,"abstract":"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.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-12-23","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}

引用次数: 0

Triazolide Complexes of Sodium and Potassium in the Gas Phase.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-23 DOI: 10.1021/acs.jpca.4c07801

Arthur E Lee, Cailum M K Stienstra, Terrance B McMahon, W Scott Hopkin

{"title":"Triazolide Complexes of Sodium and Potassium in the Gas Phase.","authors":"Arthur E Lee, Cailum M K Stienstra, Terrance B McMahon, W Scott Hopkin","doi":"10.1021/acs.jpca.4c07801","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07801","url":null,"abstract":"Aromatic organometallic complexes, such as ferrocene and the \"inverse sandwich complex\" [Na2Cp]+, are stabilized via charge-transfer (C-T) interactions and cation-π interactions (i.e., charge-induced dipole and charge-quadrupole interactions). Much effort has gone into investigating systems that contain organic moieties, such as benzene or cyclopentadienyl ligands, but less attention has been paid to aromatic systems that contain heteroatoms (e.g., N), possibly owing to the complexity arising from a lowering of symmetry and the introduction of electron lone pair density and dipole moments. Here we investigate sodiated and potassiated clusters of 1,2,3-triazolide, [Mx (123T)x-1]+ (x = 3, 4; M = Na, K), and 1,2,4-triazolide, [Mx (124T)x-1]+ (x = 3, 4; M = Na, K), using a combination of infrared ion spectroscopy (IRIS) and DFT calculations. Cluster structures are strongly influenced by charge-dipole interactions and C-T interactions from N lone pairs to the metal cations. IRIS spectra indicated that the geometries of the triazolide moieties are essentially unperturbed by the interaction with the metal ions. Additional spectral features, not predicted by DFT calculations, that are observed in the 1500-1800 cm-1 region seem to be associated with combination bands involving C-H wagging and ring torsion motions.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875351","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

Analysis of the MODIST Sequence for Selective Proton-Proton Recoupling.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-22 DOI: 10.1021/acs.jpca.4c05102

Evgeny Nimerovsky, Marianna Stampolaki, Abel Cherian Varkey, Stefan Becker, Loren B Andreas

{"title":"Analysis of the MODIST Sequence for Selective Proton-Proton Recoupling.","authors":"Evgeny Nimerovsky, Marianna Stampolaki, Abel Cherian Varkey, Stefan Becker, Loren B Andreas","doi":"10.1021/acs.jpca.4c05102","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c05102","url":null,"abstract":"Theoretical and simulated analyses of selective homonuclear dipolar recoupling sequences serve as primary tools for understanding and determining the robustness of these sequences under various conditions. In this article, we investigate the recently proposed first-order dipolar recoupling sequence known as MODIST (Modest Offset Difference Internuclear Selective Transfer). We evaluate the MODIST transfer efficiency, assessing its dependence on rf-field strengths and the number of simulated spins, extending up to 10 spins. This helps to identify conditions that enhance polarization transfer among spins that are nearby in frequency, particularly among aliphatic protons. The exploration uncovers a novel effect for first-order selective recoupling sequences that we term \"facilitated dipolar recoupling\". This effect amplifies the recoupled dipolar interaction between distant spins due to the presence of additional strongly dipolar-coupled spins. Unlike the third spin-assisted recoupling mechanism, facilitated dipolar recoupling only requires a coupling to one of the two distant spins of interest. Experimental demonstration of MODIST, including at different rf-field strengths, was carried out with the membrane protein influenza A M2 in lipid bilayers using 55 kHz magic-angle spinning (MAS). Reducing MODIST rf-field strength by a factor of 2 unveils possibilities for detecting Hα-Hα and HMeth-HMeth correlations with a 3D (H)C(H)(H)CH experiment under fast MAS rates, all achievable without specific spin labeling.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875489","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

Predicting Magnetic Barriers in Lanthanide Complexes with Electrostatic Potential Charges.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-22 DOI: 10.1021/acs.jpca.4c08008

Samuel A Fosu, Vsevolod D Dergachev, Daria D Nakritskaia, Thomas J Summers, Sergey A Varganov, David C Cantu

{"title":"Predicting Magnetic Barriers in Lanthanide Complexes with Electrostatic Potential Charges.","authors":"Samuel A Fosu, Vsevolod D Dergachev, Daria D Nakritskaia, Thomas J Summers, Sergey A Varganov, David C Cantu","doi":"10.1021/acs.jpca.4c08008","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c08008","url":null,"abstract":"Single-molecule magnets (SMMs) with slow relaxation of magnetization and blocking temperatures above that of liquid nitrogen are essential for practical applications in high-density data storage devices and quantum computers. A rapid and accurate prediction of the effective magnetic relaxation barrier (Ueff) is needed to accelerate the discovery of high-performance SMMs. Using density functional theory and multireference calculations, we explored correlations between Ueff, partial atomic charges, and the anisotropic barrier for a series of sandwich-type lanthanide complexes containing cyclooctatetraene, substituted cyclopentadiene, phospholyl, boratabenzene, or borane ligands. Our results show a correlation between the electrostatic potential charge of the lanthanide ion in the complex and Ueff. Systematic ligand modifications show that reducing ligand nucleophilicity and incorporating soft bases enhance magnetic anisotropy and Ueff values. This work identifies a correlation to predict Ueff values and optimization of ligand coordination environments in lanthanide-based SMMs.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875413","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

Balance of Unimolecular and Bimolecular Pathways Control the Temperature-Dependent Kinetics of Ozonolysis in Aerosols.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-21 DOI: 10.1021/acs.jpca.4c06885

Ryan S Reynolds, Kevin R Wilson

{"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":"https://doi.org/10.1021/acs.jpca.4c06885","url":null,"abstract":"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 (γeff) are obtained from the multiphase reaction kinetics, which are quantified by Vacuum Ultraviolet Photoionization Aerosol Mass Spectrometry. For aerosols composed of only of alkenes, γeff 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), γeff 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.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-12-21","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}

引用次数: 0

Temperature-Dependent Reaction Kinetics of the Carbanions C_n^- and C_nH^- (n = 2 and 4) with H Atoms in a Cryogenic Ion Trap.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-20 DOI: 10.1021/acs.jpca.4c06626

Christine Lochmann, Sruthi Purushu Melath, Michael Hauck, Robert Wild, Roland Wester

引用次数: 0

Experimental and Theoretical Study on Electron Interactions with Acetic Acid Molecules.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-20 DOI: 10.1021/acs.jpca.4c07838

Natalia Tańska, Kuba Wójcik, Thiago Corrêa Freitas, Márcio H F Bettega, Czesław Szmytkowski, Paweł Możejko

引用次数: 0

Assessing Computational Methods to Calculate the Binding Energies of Dimers of Five-Membered Heterocyclic Molecules.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-19 Epub Date: 2024-12-10 DOI: 10.1021/acs.jpca.4c05409

Alhadji Malloum, Jeanet Conradie

{"title":"Assessing Computational Methods to Calculate the Binding Energies of Dimers of Five-Membered Heterocyclic Molecules.","authors":"Alhadji Malloum, Jeanet Conradie","doi":"10.1021/acs.jpca.4c05409","DOIUrl":"10.1021/acs.jpca.4c05409","url":null,"abstract":"Computational electronic structure methods, including ab initio and density functional theory (DFT), have been assessed in calculating the binding energies of 14 five-membered heterocyclic dimers. The configurations were generated using classical molecular dynamics before optimization at the MP2/aug-cc-pVTZ. Benchmark binding energies are calculated at the CCSD(T)/CBS level of theory. Among the ab initio methods, the DLPNO-CCSD(T)/CBS method has the best performance, reproducing CCSD(T)/CBS with a mean absolute deviation (MAD) of 0.17 kcal/mol. In addition, a schematic CCSD(T)/CBS approach perfectly reproduces the canonical CCSD(T)/CBS with a mean absolute error of 0.08 kcal/mol. Regarding DFT functionals, it has been found that counterpoise corrections have negligible effects on the accuracy of the functionals. Furthermore, including the D3 empirical dispersion considerably enhances the accuracy of the DFT functionals. As a result, outstanding performance is noted for the double hybrid functional B2K-PLYP, with a mean absolute error of 0.25 kcal/mol. In addition to the B2K-PLYP double hybrid functional, M05-D3, B97D, M05-2X-D3, M05-2X, M06-HF, M08-HX, M11, TPSSh-D3, and RSX-0DH-D3(BJ) have MAD values lower than 0.5 kcal/mol. These functionals are recommended for further investigations of five-membered heterocyclic clusters.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"10775-10784"},"PeriodicalIF":2.7,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142805540","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

A Tribute to Gustavo E. Scuseria.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-12-19 DOI: 10.1021/acs.jpca.4c07208

Matthias Ernzerhof, Troy Van Voorhis, Viktor N Staroverov

引用次数: 0