The Journal of Physical Chemistry A最新文献_第4页

Geometrical Structures of Platinum Oxide Cluster Anions Studied by Ion Mobility-Mass Spectrometry 离子迁移-质谱法研究氧化铂簇阴离子的几何结构。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-14 DOI: 10.1021/acs.jpca.5c04493

Yuto Nakajima, , , M. Abdul Latif, , , Toshiaki Nagata, , , Keijiro Ohshimo, , and , Fuminori Misaizu*,

{"title":"Geometrical Structures of Platinum Oxide Cluster Anions Studied by Ion Mobility-Mass Spectrometry","authors":"Yuto Nakajima, , , M. Abdul Latif, , , Toshiaki Nagata, , , Keijiro Ohshimo, , and , Fuminori Misaizu*, ","doi":"10.1021/acs.jpca.5c04493","DOIUrl":"10.1021/acs.jpca.5c04493","url":null,"abstract":"Geometrical structures of platinum oxide cluster anions were investigated using ion mobility-mass spectrometry and compared with their cationic counterparts obtained from our previous study. The measured collision cross sections (CCSs) with He under 170 K of PtnOn– anions were larger than those of PtnOn+ cations, suggesting that the anions adopt more extended structures than their cationic analogues. In particular, planar Pt frameworks with bridging oxygen atoms were predicted for PtnOn– (n = 4–7), based on the agreement between the experimental CCS values and those in theoretical calculations. For n = 4 and 5, these structures are consistent with the lowest-energy geometries reported for the corresponding neutral clusters. In contrast, the cationic species adopt three-dimensional structural motifs for n ≥ 5. The assigned structures and natural bond orbital (NBO) charge analyses indicate that increased electron density on the Pt framework stabilizes the planar configurations in the anions, leading to larger CCSs.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9658–9666"},"PeriodicalIF":2.8,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285071","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

Infrared Spectroscopy of Radical-Cation Clusters (NH3)n=4–6+ 自由基-阳离子团簇（NH3）n=4-6的红外光谱。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-14 DOI: 10.1021/acs.jpca.5c05309

Amandeep Singh, , , Arisa Iguchi, , , Zane Golpariani, , , Tom C. Bernaards, , , Asuka Fujii, , , Hajime Tanuma, , , Toshiyuki Azuma, , , Kenta Mizuse*, , , Susumu Kuma*, , and , Andrey F. Vilesov*,

{"title":"Infrared Spectroscopy of Radical-Cation Clusters (NH3)n=4–6+","authors":"Amandeep Singh, , , Arisa Iguchi, , , Zane Golpariani, , , Tom C. Bernaards, , , Asuka Fujii, , , Hajime Tanuma, , , Toshiyuki Azuma, , , Kenta Mizuse*, , , Susumu Kuma*, , and , Andrey F. Vilesov*, ","doi":"10.1021/acs.jpca.5c05309","DOIUrl":"10.1021/acs.jpca.5c05309","url":null,"abstract":"Radical-cation clusters of ammonia ((NH3)n=4–6+) were produced inside helium droplets and studied via infrared laser spectroscopy in the NH stretching region. The clusters have multiple isomers, whose structures were studied with quantum chemical calculations. The comparison of the measured and calculated spectra of the free NH stretches shows that each cluster has an NH4+ core, solvated by NH3 molecules and an NH2 radical through hydrogen bonds, as their respective global minima states. The spectra of (NH3)n=4–6+ contain the arrays of strong bands in the frequency range of 2300–3200 cm–1, which stem from the interaction between the hydrogen bond bridge vibrations of the ammonium core NH4+ and the overtones of its bending modes. The spectra of (NH3)5+ and (NH3)6+ indicate the presence of some additional higher-energy isomers, which have a free NH stretch of the NH4+ core.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9721–9732"},"PeriodicalIF":2.8,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285061","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

Bond Dissociation Energies, Proton, Hydride, Electron Affinities, and Ionization Potentials of C1 Hydrocarbon Ions 碳氢化合物C1离子的键解离能、质子、氢化物、电子亲和和电离势。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-14 DOI: 10.1021/acs.jpca.5c03502

Yiwei Gong, and , Florian F. Mulks*,

引用次数: 0

Vibrational Spectroscopy of Triple 13C18O15N Isotope-Edited N-Methylacetamide: Interplay between Experiment and Theory (IR, Raman, UVRR) 三联13C18O15N同位素编辑n -甲基乙酰胺的振动光谱：实验与理论的相互作用（IR, Raman， UVRR）。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c03637

Luca Supovec, , , Sara Gómez, , , Tommaso Giovannini, , , Chiara Cappelli*, , and , Sebastian Schlücker*,

{"title":"Vibrational Spectroscopy of Triple 13C18O15N Isotope-Edited N-Methylacetamide: Interplay between Experiment and Theory (IR, Raman, UVRR)","authors":"Luca Supovec, , , Sara Gómez, , , Tommaso Giovannini, , , Chiara Cappelli*, , and , Sebastian Schlücker*, ","doi":"10.1021/acs.jpca.5c03637","DOIUrl":"10.1021/acs.jpca.5c03637","url":null,"abstract":"Isotope editing of amide bonds is a powerful tool for site-specific vibrational spectroscopy of peptides and proteins. However, only single and double isotope labeling such as 13C18O and 13C15N has been reported so far. Here, we establish triple 13C118O15N isotope editing of the amide bond in N-methylacetamide (NMA) as the most widely employed model system for peptides. The effect of successive isotope labeling on the peak position of amide modes is systematically studied by comparing the IR, electronically nonresonant Raman, and UV resonance Raman (UVRR) spectra of NMA-13C1, NMA-13C118O, and NMA-13C118O15N. The experimental spectra agree well with theoretical predictions obtained by using atomistic, fully polarizable multiscale quantum mechanical (QM)/classical modeling of neat NMA (IR/Raman) and NMA in aqueous solution (UVRR). The presented triple-labeling approach paves the way for complementary site-specific studies of individual amide bonds and their prominent amide I, II, and III vibrations by using both IR and UVRR spectroscopy on the same 13C18O15N-labeled sample.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9777–9787"},"PeriodicalIF":2.8,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285018","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

Implementation of McMurchie–Davidson Algorithm for Gaussian AO Integrals Suited for SIMD Processors 适用于SIMD处理器的高斯AO积分的mcmurkie - davidson算法的实现。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c04136

Andrey Asadchev, and , Edward F. Valeev*,

{"title":"Implementation of McMurchie–Davidson Algorithm for Gaussian AO Integrals Suited for SIMD Processors","authors":"Andrey Asadchev,  and , Edward F. Valeev*, ","doi":"10.1021/acs.jpca.5c04136","DOIUrl":"10.1021/acs.jpca.5c04136","url":null,"abstract":"We report an implementation of the McMurchie–Davidson evaluation scheme for 1- and 2-particle Gaussian AO integrals designed for processors with Single Instruction Multiple Data (SIMD) instruction sets. Like in our recent MD implementation for graphical processing units (GPUs) [<contrib-group>Asadchev, A.; Valeev, E. F.</contrib-group>. <cite>J. Chem. Phys.</cite> 2024, 160, <elocation-id>244109</elocation-id>.], variable-sized batches of shellsets of integrals are evaluated at a time. By optimizing for the floating point instruction throughput rather than minimizing the number of operations, this approach achieves up to 50% of the theoretical hardware peak FP64 performance for many common SIMD-equipped platforms (AVX2, AVX512, NEON), which translates to speedups of up to 30 over the state-of-the-art one-shellset-at-a-time implementation of Obara–Saika-type schemes in Libint for a variety of primitive and contracted integrals. As with our previous work, we rely on the standard C++ programming language─such as the std::simd standard library feature to be included in the 2026 ISO C++ standard─without any explicit code generation to keep the code base small and portable. The implementation is part of the open source LibintX library freely available at https://github.com/ValeevGroup/libintx.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9788–9797"},"PeriodicalIF":2.8,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c04136","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285057","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}

引用次数: 0

Spin-Flip TDDFT within the Sternheimer Formulation: A Gaussian and Plane Wave Implementation Sternheimer公式中的自旋翻转TDDFT：高斯平面波实现。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c05234

Luis I. Hernandez-Segura*, and , Sandra Luber,

{"title":"Spin-Flip TDDFT within the Sternheimer Formulation: A Gaussian and Plane Wave Implementation","authors":"Luis I. Hernandez-Segura*,  and , Sandra Luber, ","doi":"10.1021/acs.jpca.5c05234","DOIUrl":"10.1021/acs.jpca.5c05234","url":null,"abstract":"We report the first implementation of spin-flip time-dependent density functional theory (SF-TDDFT) within the Tamm-Dancoff approximation in the Sternheimer formulation including the use of the noncollinear kernel. The noncollinear kernel was stabilized by introducing a screening method for the numerical integration, realizing a robust scheme of excited energy and gradient calculations of SF-TDDFT using generalized gradient approximation functionals. The implementation is evaluated by benchmark calculations of vertical excitation energies and optimized molecular geometries. The benchmark for vertical excitations consists of 19 excitations with high level of theory reference data from the QUESTDB. An underestimation of vertical excitation energies was observed for the PBE and PBE0 functionals, as seen by their average deviations of −0.3 eV. The benchmark for optimized geometries consists of 25 optimized structures with high level of theory, comprising CCSD, CISD, and FCI data, and 10 reference structures optimized with other implementations of collinear and noncollinear SF-TDDFT. The optimized structures using PBE and PBE0, with a noncollinear kernel, were found to be close to the high-level reference structures, with mean deviations of 0.010 and −0.004 Å, respectively. The extension to the auxiliary density matrix method (ADMM) is also presented. We found an average deviation of 0.003 Å in the calculated bond lengths when employing the ADMM for the PBE0 functional.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9798–9809"},"PeriodicalIF":2.8,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c05234","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285049","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}

引用次数: 0

Ab Initio Study on the Electronic Structure and Spectroscopic Properties of Lanthanum Monohydride (LaH) 一氢化镧（LaH）电子结构和光谱性质的从头算研究。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c06003

Shan Sun, , , Yufeng Gao*, , and , Zunlue Zhu*,

引用次数: 0

Theoretical Studies on the Competing Reaction Mechanisms of Phosphine-Catalyzed Annulation of Benzofuran-Derived Azadienes with Allyl Carbonates: [2 + 4] versus [4 + 2] 膦催化苯并呋喃衍生氮杂烯与碳酸烯酯环化竞争反应机理的理论研究：[2 + 4]与[4 + 2]。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c05139

Chunhui Liu*, , , Yongyuan Li, , , Haodi Guo, , , Suxiang Ge, , , Dapeng Li, , and , Peilin Han*,

{"title":"Theoretical Studies on the Competing Reaction Mechanisms of Phosphine-Catalyzed Annulation of Benzofuran-Derived Azadienes with Allyl Carbonates: [2 + 4] versus [4 + 2]","authors":"Chunhui Liu*, , , Yongyuan Li, , , Haodi Guo, , , Suxiang Ge, , , Dapeng Li, , and , Peilin Han*, ","doi":"10.1021/acs.jpca.5c05139","DOIUrl":"10.1021/acs.jpca.5c05139","url":null,"abstract":"Spiro[benzofuran-cyclohexane] skeletons are intriguing structural motifs in organic chemistry, and synthetic chemists employ a variety of strategies that typically involve the formation of the spirocyclic center through cyclization or ring-closing reactions. However, predicting the possible mechanisms and origin of stereoselectivity in these reactions remains a challenge. In this study, we conducted a theoretical investigation into the competing mechanisms involving phosphine-catalyzed [2 + 4] and [4 + 2] annulation processes of benzofuran-derived azadienes (BDAs) with allyl carbonates and ynals. Our calculations revealed that the [2 + 4] annulation is more energetically favorable compared to the [4 + 2] annulation. For the mechanism of [2 + 4] annulation, phosphine initially undergoes nucleophilic attack on the allyl carbonate, resulting in the formation of a phosphorus ylide accompanied by the elimination of BocO–. Subsequently, the t-BuO– species acquires a proton from the phosphorus ylide, followed by an intermolecular Michael addition with BDAs. This is then followed by intramolecular cyclization to form a cyclohexatone structure. Finally, the cyclohexatone undergoes t-BuOH assisted enolization, resulting in the formation of the spiro[benzofuran-cyclohexane] derivative, accompanied by the release of the PEt2Ph catalyst molecule. To elucidate the origin of diastereoselectivity, we also performed noncovalent interaction (NCI), atoms in molecules (AIM) analyses, and energy decomposition analysis (EDA). These investigations offer valuable insight into the general principles and detailed mechanisms underlying the synthesis of spiro[benzofuran-cyclohexane] skeletons with unique diastereoselectivity.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 42","pages":"9712–9720"},"PeriodicalIF":2.8,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285077","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

Charge Distribution and Lithium Oxide Stability Modeled by Reactive Force Field. 反作用力场模拟的电荷分布与锂氧化物稳定性。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-13 DOI: 10.1021/acs.jpca.5c03998

Vjeran Gomzi, Jakov Juvančić

{"title":"Charge Distribution and Lithium Oxide Stability Modeled by Reactive Force Field.","authors":"Vjeran Gomzi, Jakov Juvančić","doi":"10.1021/acs.jpca.5c03998","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03998","url":null,"abstract":"Understanding the reactive properties of lithium and its oxides plays an important role in the modeling and design of lithium batteries. For the investigation of reasonably large structures, the use of molecular dynamics is usually the method of choice because of its calculation efficiency. The shortcoming of this approach is that the electron distribution is approximated by parameters obtained semiempirically or approximated at different levels from first-principles calculations. A novel method based on Kohn-Sham density functional theory, approximated to the second order (ACKS2), for modeling the charge distribution has recently been introduced. The method resolves two major problems from which the previous electronegativity equilibration method suffers, although some shortcomings remain. Here, we first verify the effect that the charge calculation method has on theoretical reproduction of the atomic charges obtained by the model, and then proceed to optimize the force field parameters in an attempt to alleviate the problems perceived. The newly trained ACKS2 reactive force field is validated and shown to be able to reproduce the structure and charge distribution of the lithium crystal and lithium-oxide crystal slabs enclosed by the vacuum layer.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285079","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

Dicationic Helium Molecular Cluster, Hen2+ (n = 4, 5): Noble Gas Analogue of Hydrocarbon 指示氦分子簇，Hen2+ (n = 4,5)：碳氢化合物的惰性气体类似物。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-10-11 DOI: 10.1021/acs.jpca.5c06707

Kangkan Sarmah, , , Farnaz Yashmin, , , Siddhartha K. Purkayastha, , , Amit Das, , , Palash J. Thakuria, , and , Ankur K. Guha*,

引用次数: 0