The Journal of Physical Chemistry A最新文献_第10页

Exploring the Coexistence of Spin States in [Fe(tpy-Ph)2]2+ Complexes on Au(111) Using DFT Calculations 利用DFT计算探索Au（111）上[Fe(tpy-Ph)2]2+配合物中自旋态的共存

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-25 DOI: 10.1021/acs.jpca.5c03161

Naveen K. Dandu, , , Alex Taekyung Lee, , , Sergio Ulloa, , , Larry Curtiss, , , Saw Wai Hla, , and , Anh T. Ngo*,

{"title":"Exploring the Coexistence of Spin States in [Fe(tpy-Ph)2]2+ Complexes on Au(111) Using DFT Calculations","authors":"Naveen K. Dandu, , , Alex Taekyung Lee, , , Sergio Ulloa, , , Larry Curtiss, , , Saw Wai Hla, , and , Anh T. Ngo*, ","doi":"10.1021/acs.jpca.5c03161","DOIUrl":"10.1021/acs.jpca.5c03161","url":null,"abstract":"In this work, we systematically study the electronic structure and stability of spin states of the [Fe-(tpy-ph)2]2+ molecule in both the gas phase and on a Au(111) substrate using density functional theory + U (DFT+U) calculations. We find that the stability of the Fe2+ ion’s spin states predicted by the computations is significantly influenced by the Hubbard U parameter. In the gas phase, the low-spin (LS, S = 0) state is found to be energetically favorable for U(Fe) ≤ 3 eV, whereas the high-spin (HS, S = 2) state is stabilized for U(Fe) > 3 eV. Interaction with the Au(111) substrate is found to elevate the critical U for the spin-state transition to 3.5 eV. Additionally, we perform L-edge X-ray absorption spectroscopy (XAS) calculations for both HS and LS states. The calculated XAS suggests that the HS state more closely aligns with the experimental observations, indicating the potential coexistence of the HS state as the initial state during the X-ray excitation process. These findings enrich our understanding of spin-state dynamics in [Fe(tpy-Ph)2]2+.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 40","pages":"9185–9194"},"PeriodicalIF":2.8,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147062","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

The Electronic Structure of Zirconium and Hafnium Monochalcogenides 单硫系锆和铪的电子结构。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-25 DOI: 10.1021/acs.jpca.5c05402

João G. F. Romeu, , , Nickolas A. Joyner, , , Elliot Kaye, , , Kirk A. Peterson*, , , Thomas T. Kawagoe, , , Samantha L. Stinson, , , Michael D. Morse*, , and , David A. Dixon*,

{"title":"The Electronic Structure of Zirconium and Hafnium Monochalcogenides","authors":"João G. F. Romeu, , , Nickolas A. Joyner, , , Elliot Kaye, , , Kirk A. Peterson*, , , Thomas T. Kawagoe, , , Samantha L. Stinson, , , Michael D. Morse*, , and , David A. Dixon*, ","doi":"10.1021/acs.jpca.5c05402","DOIUrl":"10.1021/acs.jpca.5c05402","url":null,"abstract":"High-level ab initio CCSD(T) and spin–orbit icMRCI+Q calculations were used to predict potential energy curves (PECs) for the lowest-lying states of ZrO, ZrS, HfO, and HfS. The prediction of the ground state is basis set dependent at the icMRCI+Q level for ZrO and ZrS due to the small singlet–triplet splitting between the lowest 1Σ+ and 3Δ states. CCSD(T) with a spin orbit correction predicted the 1Σ+ ground state in agreement with experiment. New all-electron basis sets were developed for Hf to improve the results over those predicted by use of effective core potentials (ECPs) that subsume the 4f electrons into the definition of the core. The use of the new DK-4f basis sets rather than ECPs became more important for HfO and HfS where there is a lack of a good core–valence separation. icMRCI+Q, CCSD(T), and DFT calculations for the spectroscopic parameters of ZrO, ZrS, HfO, and HfS were benchmarked with available experimental data. Bond dissociation energies (BDEs) of these four systems were calculated at the Feller–Peterson–Dixon (FPD) level to be 762.1 (ZrO), 543.5 (ZrS), 803.8 (HfO), and 575.1 kJ/mol (HfS), in excellent agreement with experiment. The HfS BDE was remeasured using the R3PI method, providing an updated experimental measurement of D0(HfS) = 5.978 ± 0.002 eV = 576.8 ± 0.2 kJ/mol. This experimental value, combined with experimental measurements of the ionization energies of Hf and HfS, gives the cationic BDE of D0(Hf+-S) = 5.124 ± 0.002 eV = 494.4 ± 0.2 kJ/mol.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 40","pages":"9325–9341"},"PeriodicalIF":2.8,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145147134","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

Automatic Molecule Fragmentation for Density Matrix Embedding Theory 基于密度矩阵嵌入理论的自动分子碎片化。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-24 DOI: 10.1021/acs.jpca.5c06027

Satoshi Imamura*, , , Naoki Iijima, , , Akihiko Kasagi, , and , Eiji Yoshida,

{"title":"Automatic Molecule Fragmentation for Density Matrix Embedding Theory","authors":"Satoshi Imamura*, , , Naoki Iijima, , , Akihiko Kasagi, , and , Eiji Yoshida, ","doi":"10.1021/acs.jpca.5c06027","DOIUrl":"10.1021/acs.jpca.5c06027","url":null,"abstract":"In quantum chemical calculations, the computational cost of highly accurate ground-state energy calculations for large-scale molecules is exceedingly high. To reduce the computational cost while sustaining high accuracy, quantum embedding methods, such as the density matrix embedding theory (DMET) and bootstrap embedding (BE), have been developed. In DMET, we need to manually determine how to fragment a target molecule, and both the accuracy and computational cost strongly depend on it. This issue hinders the easy application of DMET to practical molecules. On the other hand, BE can be easily applied to any molecules because it automatically constructs fragments based on the structure of a target molecule. In this work, we propose a graph-based automatic molecule fragmentation (GAF) technique to enable the easy application of DMET and evaluate the accuracy and wall-clock time of DMET applying the proposed technique (GAF-DMET) and the atom-based BE (ABE) for a wide variety of molecules on a cluster system. GAF represents a molecular structure with an undirected graph where edge weights represent interatomic interactions and determines an accurate fragmentation pattern by solving a graph partitioning problem that minimizes the total weight of edges cut. For GAF, we present two metrics to accurately represent interatomic interactions in different basis sets and the automatic adjustment of the number of fragments. The evaluation for 14 small molecules shows that (1) GAF successfully selects accurate fragmentation patterns, and (2) GAF-DMET can achieve higher or comparable accuracy than ABE in shorter wall-clock times. Moreover, we demonstrate that GAF-DMET is more accurate than ABE in two use cases: binding energy calculations between middle and small molecules, and an SN2 reaction.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 40","pages":"9511–9520"},"PeriodicalIF":2.8,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c06027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129613","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

Kinetic Investigations of the OH-Initiated Reactions of Methyl Cyclohexene Isomers in the Troposphere: An Experimental and Computational Study. 对流层中甲基环己烯同分异构体oh引发反应的动力学研究：实验与计算研究。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-24 DOI: 10.1021/acs.jpca.5c03646

Gopika S Madhu, Balla Rajakumar

{"title":"Kinetic Investigations of the OH-Initiated Reactions of Methyl Cyclohexene Isomers in the Troposphere: An Experimental and Computational Study.","authors":"Gopika S Madhu, Balla Rajakumar","doi":"10.1021/acs.jpca.5c03646","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03646","url":null,"abstract":"Kinetic investigations of two isomers of methyl cyclohexene (1-methyl cyclohexene, 1MCHXE, and 4-methyl cyclohexene, 4MCHXE) with OH radical over the temperature range 263-363 K employing experimental and theoretical methodologies were performed in this study. The pulsed laser photolysis-laser-induced fluorescence technique was employed for the experimental studies. The obtained temperature-dependent rate coefficients for the OH-initiated reactions of 1MCHXE and 4MCHXE are k(263-363 K) = (2.09 ± 0.65) × 10-11 exp{(388 ± 96)/T} and k(263-363 K) = (6.49 ± 1.34) × 10-12 exp{(462 ± 63)/T} cm3 molecule-1 s-1, respectively. Computational studies were conducted using CVT/SCT/ISPE with the aid of Gaussian 16 and POLYRATE 17-C software. 1MCHXE exhibited higher reactivity than 4MCHXE, both experimentally and theoretically. The reason behind this increase in the rate coefficient is discussed in terms of the position of the methyl group with respect to the unsaturated double bond. The thermodynamic and kinetic feasibilities of different reaction pathways were investigated in detail. Branching ratios and Fukui functions for radical attack were calculated to support the site-specific reactivity followed by the OH-initiated reaction pathways. Since methyl cyclohexene is released from a variety of natural and manmade sources and serves as a model for a large number of biogenic terpene compounds, atmospheric implication parameters such as lifetime and photochemical ozone creation potential of its isomers were determined.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129596","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

Density Functional Theory for Molecular and Periodic Systems in TURBOMOLE: Theory, Implementation, and Applications TURBOMOLE中分子和周期系统的密度泛函理论：理论、实现和应用。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-23 DOI: 10.1021/acs.jpca.5c02937

Manas Sharma, , , Yannick J. Franzke, , , Christof Holzer, , , Fabian Pauly, , and , Marek Sierka*,

{"title":"Density Functional Theory for Molecular and Periodic Systems in TURBOMOLE: Theory, Implementation, and Applications","authors":"Manas Sharma, , , Yannick J. Franzke, , , Christof Holzer, , , Fabian Pauly, , and , Marek Sierka*, ","doi":"10.1021/acs.jpca.5c02937","DOIUrl":"10.1021/acs.jpca.5c02937","url":null,"abstract":"This work provides a detailed overview of density functional theory (DFT) methods for treating molecular and periodic systems within the TURBOMOLE software package. The implementation employs Gaussian-type orbitals and is based on efficient real-space techniques and density-fitting approaches for Coulomb interactions. Recent developments are reviewed, including the treatment of relativistic effects with effective core potentials, the incorporation of spin–orbit coupling via two-component formalisms, and the extension to real-time time-dependent DFT (RT-TDDFT). Embedding schemes based on frozen-density and projection-based approaches are also discussed, enabling the combination of DFT with high-level correlated wave function methods and many-body perturbation theory for selected subsystems. Representative applications demonstrate the capabilities across bulk materials, surfaces, low-dimensional nanostructures, and adsorption processes. Additionally, a web-based graphical interface has been developed to support input generation, structure manipulation, and output analysis. By consolidating theoretical foundations, implementation strategies, and application examples, this work provides a reference for the use of periodic DFT methods in quantum chemical and materials science studies.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 39","pages":"9062–9083"},"PeriodicalIF":2.8,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c02937","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123820","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

Revisiting the Spin–Lattice Relaxation of Homonuclear In-Phase and Antiphase NMR Magnetization 重温同核正相和反相核磁共振磁化的自旋-晶格弛豫。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-23 DOI: 10.1021/acs.jpca.5c05247

Lauren M. Kehoe, , , Zachary G. Mayes, , , Kelsey E. Brakensiek, , , Emma L. Ellis, , , Adam J. Alderfer, , , Lingyu Chi, , and , Klaus Woelk*,

{"title":"Revisiting the Spin–Lattice Relaxation of Homonuclear In-Phase and Antiphase NMR Magnetization","authors":"Lauren M. Kehoe, , , Zachary G. Mayes, , , Kelsey E. Brakensiek, , , Emma L. Ellis, , , Adam J. Alderfer, , , Lingyu Chi, , and , Klaus Woelk*, ","doi":"10.1021/acs.jpca.5c05247","DOIUrl":"10.1021/acs.jpca.5c05247","url":null,"abstract":"Hyperpolarization techniques such as dynamic nuclear polarization (DNP), chemically-induced dynamic nuclear polarization (CIDNP), and parahydrogen-induced polarization (PHIP) enhance the sensitivity of NMR spectroscopy and MRI, but the associated antiphase magnetization patterns often relax faster than those of conventional in-phase signals. This study analyzes the spin–lattice relaxation matrix for single-quantum transitions in an isolated, weakly coupled two-spin AX system to identify eigenvectors and eigenvalues that govern the time evolution of in-phase and antiphase longitudinal magnetization. The analysis predicts that AX antiphase magnetization, such as that generated by PHIP hydrogenations in high magnetic field, can relax up to twice as fast as the in-phase magnetization of traditional inversion-recovery or saturation-recovery experiments. To validate these predictions, a dedicated NMR pulse sequence was used to selectively generate and monitor antiphase magnetization. trans-Cinnamic acid in deuterated DMSO served as a model compound, with the hydrogen atoms on its central conjugated double bond forming a weakly coupled AX spin system with a large scalar coupling (>16 Hz). The large scalar coupling allowed for the separate integration of the two lines in each doublet. Experimental results confirm an accelerated relaxation of antiphase magnetization but also reveal that in-phase relaxation is influenced by double-quantum transitions, which do not contribute to the relaxation of antiphase magnetization. The findings of this study highlight the importance of distinguishing in-phase from antiphase relaxation, providing a basis for optimizing hyperpolarization experiments with explicit consideration of antiphase signal dynamics.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 39","pages":"8993–9000"},"PeriodicalIF":2.8,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129622","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

Theoretical Study on the Structure and Electronic Excited States of the FNO Molecule FNO分子结构和电子激发态的理论研究。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-22 DOI: 10.1021/acs.jpca.5c00885

Shimin Shan, , , Hongjing Liang, , , Zirun Li, , , Huifang Zhao, , , Haifeng Xu*, , and , Bing Yan*,

引用次数: 0

Ground and Excited States of 3d and 4d Transition Metals: Computational Insight into Atomic Properties 三维和四维过渡金属的基态和激发态：对原子性质的计算洞察力。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-22 DOI: 10.1021/acs.jpca.5c05650

Ebtisam M. Z. Telb, , , Nuno M. S. Almeida, , , Bradley K. Welch, , and , Angela K. Wilson*,

引用次数: 0

Calculated Magnetic and Geometric Structures of Neutral Copper Oxide Clusters 计算中性氧化铜团簇的磁性和几何结构。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-22 DOI: 10.1021/acs.jpca.5c04015

Chase H. Rotteger, , , Hannah G. Rucker, , , Madison M. Sobol, , and , Scott G. Sayres*,

{"title":"Calculated Magnetic and Geometric Structures of Neutral Copper Oxide Clusters","authors":"Chase H. Rotteger, , , Hannah G. Rucker, , , Madison M. Sobol, , and , Scott G. Sayres*, ","doi":"10.1021/acs.jpca.5c04015","DOIUrl":"10.1021/acs.jpca.5c04015","url":null,"abstract":"The ground state geometric structures and electron configurations of subnanometer neutral copper oxide clusters are calculated with density functional theory. By comparing the results across almost 40 clusters, ranging between Cu3O3 and Cu16O8, we find evidence for strong ferromagnetic coupling that is responsible for increasing the number of unpaired electrons as Cu atoms are incremented away from the (Cu2O)n stoichiometry. The closed-shell (Cu2O)n clusters are nonmagnetic, whereas all other clusters exhibit varying degrees of magnetic susceptibility. The majority of the clusters considered in this manuscript have not been previously evaluated. Natural bonding orbital and Bader charge analysis reveal a nearly linear correlation between the charge transfer between Cu and O atoms and their local spin magnetic moments. Further, a relationship between the coordination of O atoms composing the cluster and their local magnetic moment is found. Bridging O atoms (μ2-O) typically exhibit large local magnetic moments, whereas the local magnetic moment is quenched by tetrahedrally coordinated (μ4-O) atoms. Thus, clusters containing Cu(II) atoms contain a large total magnetic moment, whereas Cu(I) atom clusters generally exhibit a small total magnetic moment and terminal Cu atom structures.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 39","pages":"8982–8992"},"PeriodicalIF":2.8,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123859","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

Questioning the Central Bond in [1.1.1]Propellane: Insights from Probability Density Analysis [1.1.1]螺旋桨中中心键的质疑：来自概率密度分析的见解。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-21 DOI: 10.1021/acs.jpca.5c03794

Michel V. Heinz, and , Arne Lüchow*,

引用次数: 0