Journal of Computational Chemistry最新文献

{"title":"Feasibility of Combining Biomolecular Conformational Sampling Techniques for Molecular Dynamics Simulation","authors":"Jinzen Ikebe,&nbsp;Hidetoshi Kono","doi":"10.1002/jcc.70192","DOIUrl":"https://doi.org/10.1002/jcc.70192","url":null,"abstract":"<p>We assess the feasibility of combining two advanced molecular dynamics techniques for efficient biomolecular conformational sampling: the generalized ensemble method for enhancing conformational sampling in partial systems (GEPS), such as ALSD and REST2, which dynamically modulate atomic charges in selected regions, and the zero-multipole summation method (ZMM), which efficiently computes electrostatic interactions assuming local electrostatic neutrality. To address whether charge variation in GEPS violates the fundamental assumption of ZMM, we compared conformational ensembles obtained using GEPS combined with either ZMM or a conventional electrostatic calculation method. Our results demonstrate that GEPS and ZMM can be effectively combined without introducing systematic bias. Additionally, we identified a potential limitation of ZMM: in highly polarized systems, it may fail to capture long-range electrostatic repulsion, potentially leading to artifacts. These findings support the practical use of GEPS with ZMM for conformational sampling; however, caution is warranted when applying ZMM to systems with highly delocalized electrostatics.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":4.8,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70192","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144725398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Assessing the Catalytic Potential of Novel ADAP-M (M = Cu, Ag, Au) Catalysts in [3 + 2] Cycloaddition Reactions","authors":"Ali A. Khairbek,&nbsp;Maha I. Al-Zaben,&nbsp;Renjith Thomas","doi":"10.1002/jcc.70194","DOIUrl":"https://doi.org/10.1002/jcc.70194","url":null,"abstract":"<div>\u0000 \u0000 <p>This study investigated the catalytic potential of novel alkoxydiaminophosphine-metal (ADAP-M, M = Cu, Ag, Au) complexes in [3 + 2] cycloaddition (32CA) reactions, specifically for synthesizing 1,2,3-triazoles through metal-assisted azide–alkyne cycloaddition (MAAC). Density functional theory (DFT) was used to evaluate the electronic and structural properties of these complexes to determine their catalytic efficiency. The ADAP ligand is crucial for reducing the activation energy and stabilizing intermediates, thereby enhancing catalysis. The study compared mononuclear and binuclear pathways and revealed that ADAP-Cu complexes, especially in binuclear forms, presented the most favorable energy profiles with significant barrier reductions due to cooperative copper interactions. In contrast, ADAP complexes with silver and gold exhibit higher activation energies and lower efficiency. The role of the solvent was also examined, revealing that toluene increases the energy barriers in metal-catalyzed reactions. These findings emphasize the superior catalytic efficiency of copper-based ADAP complexes and the impact of solvent choice on reaction dynamics, offering insights for advanced catalytic system design in organic synthesis.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exhaustive Spatial Sampling for Complete Topology of the Electrostatic Potential","authors":"Evelio Francisco,&nbsp;Ángel Martín Pendás,&nbsp;Dimas Suárez","doi":"10.1002/jcc.70188","DOIUrl":"https://doi.org/10.1002/jcc.70188","url":null,"abstract":"<p>This work presents a robust and efficient algorithm for exhaustively determining the critical points (CPs) of the molecular electrostatic potential (MEP) in 3D space. By combining Newton's method with a systematic physical space sampling strategy, we locate all CPs (maxima, minima, and saddle points) for both exact quantum-chemical MEPs and their tricubic interpolated approximations. The method is validated using a test function with known CPs and applied to a diverse set of molecules, including neutral systems, ions, and noncovalent complexes from the S66 and IONIC-HB datasets. Our results demonstrate that the interpolated MEP faithfully reproduces the topology of the exact potential in most cases, with minor discrepancies arising near nuclear positions or in regions of low gradient. The algorithm's efficiency (2–7<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mo>×</mo>\u0000 </mrow>\u0000 <annotation>$$ times $$</annotation>\u0000 </semantics></math> faster for interpolated calculations) and robustness make it suitable for large-scale analyses of MEP topologies, offering insights into chemical reactivity and noncovalent interactions.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70188","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Peri-Fused Six-Membered Cyclic Nitrenium Ions (PCNIs): Electronic Structure and Aromaticity","authors":"Lahu N. Dayare,&nbsp;Astha Gupta,&nbsp;Kanika Manchanda,&nbsp;Prasad V. Bharatam","doi":"10.1002/jcc.70197","DOIUrl":"https://doi.org/10.1002/jcc.70197","url":null,"abstract":"<div>\u0000 \u0000 <p>Cyclic nitrenium ions (CNIs) with five and seven-membered rings are well known, but the CNIs with six-membered rings are rare. Only a few are known as peri-fused six-membered cyclic nitrenium ions (PCNIs) and they are reported to be nitrogen Lewis acids. Preliminary electronic structure analysis indicated that the electronic properties of PCNIs somewhat deviate from the other CNIs (five or seven-membered). Further, these ring systems proved to be non-aromatic (in the triazine ring), whereas the five and seven-membered analogs are aromatic. In this work, an electronic structure analysis was carried out on the newly designed PCNIs to understand their characteristic features. Several analogs of these species were designed to identify PCNIs with improved electronic stability. The PCNIs are electrophilic because of the empty p orbital and the formal positive charge at the central nitrogen atom. The Lewis acidic character of known and designed PCNIs has been evaluated in terms of hydride ion affinity (HIA), fluoride ion affinity (FIA), ΔH_PMe3 and ΔH_NHC values. This work helped identify a set of new PCNIs whose electronic stability and Lewis acidity parameters are significantly high. Further, a few of these systems were found to be aromatic in all three rings with notable negative NICS(1) values.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revealing the Effect of Hindered Weak Electrostatic Interactions of the Alkane Chain Length in the Imidazolium Chloride Ionic Liquids: A Molecular Electrostatic Potential Study","authors":"Mary S. Richardson,&nbsp;Ava Augustine,&nbsp;Nilesh R. Dhumal","doi":"10.1002/jcc.70196","DOIUrl":"https://doi.org/10.1002/jcc.70196","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;p&gt;The molecular electrostatic potential (MEP) provides the electron-rich and deficient regions within the molecular system, which enables the prediction of the noncovalent electrostatic interactions with other molecules. The alkane group attached to the nitrogen atom of the imidazolium ring plays an important role in the stabilization of ion pairs through electrostatic interactions such as hydrogen bonding. An inverse correlation between the &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;C&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;H&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;C&lt;/mi&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mtext&gt;⋯&lt;/mtext&gt;\u0000 &lt;msup&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;Cl&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{C}}_2-{mathrm{H}}_{C2}cdots {mathrm{C}mathrm{l}}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; distance and the MEP at minimum near the &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;Cl&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{Cl}}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; anion revealed the presence of weak noncovalent electrostatic interactions between the positive potential of alkane chain hydrogen and the electron density of the &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;Cl&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{Cl}}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; anion. Consequently, a blue shift is noticed for &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mtext&gt;C&lt;/mtext&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 ","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extension of Composite Method and Machine-Learned Electron Correlation Model to Fourth-Period Elements","authors":"Ryo Fujisawa,&nbsp;Mikito Fujinami,&nbsp;Hiromi Nakai","doi":"10.1002/jcc.70191","DOIUrl":"https://doi.org/10.1002/jcc.70191","url":null,"abstract":"<div>\u0000 \u0000 <p>Accurate and efficient correlation energy calculation is a major challenge in quantum chemistry. We propose an extended machine-learned electron correlation (ML-EC) model that estimates CCSD(T)/CBS correlation energy using descriptors from Hartree-Fock (HF) calculations with double-zeta basis sets. While the previous ML-EC model was limited to third-period elements, we extend it to fourth-period elements by modifying the composite method parameters. The optimized parameters accurately reproduce CCSD(T)/CBS correlation energies and correlation energy densities. Trained on G3/05 dataset molecules, the ML-EC model accurately predicts CCSD(T)/CBS correlation energies for test molecules. Reaction energies computed with the ML-EC model surpass DFT methods in accuracy. Additionally, the ML-EC model significantly reduces computational cost, achieving a speedup of over 50 times compared to conventional CCSD(T)/CBS calculations. These results demonstrate that the extended ML-EC model is a reliable and efficient method for correlation energy calculations, particularly for systems containing heavy elements.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144717042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Tailoring Approach (MTA) Assisted Density Functional Theory Study for Large Core and Core-Shell Nanocluster Quantum Dots","authors":"Anant D. Kulkarni","doi":"10.1002/jcc.70189","DOIUrl":"https://doi.org/10.1002/jcc.70189","url":null,"abstract":"<div>\u0000 \u0000 <p>Molecular fragmentation-based method, viz. molecular tailoring approach (MTA) was employed with density functional framework to investigate prototype medium and large sized semiconductor quantum dots (QDs) of (CdSe)_n, <i>n</i> = 33, 66, 99, 146, and 185 typically of size 1.5–2.7 nm. The trends computed for structural parameters and the band gap energies of prototype structures show a good agreement with those reported earlier for <i>n</i> ≤ 99. In order to study the effect of surface passivation, we use a representative model where 2-coordinated surface atoms of (CdSe)_n QDs were saturated by hydrogen atoms. The prototype for passivated nanoclusters shows enhancement of band gap energy over their bare (CdSe)_n counterparts. We further highlight the strength of our approach by extending the study for the modeled nanoclusters larger than 2.2 nm size, viz. (CdSe)₁₄₆ (diameter d = 2.5 nm), (CdSe)₁₈₅ (d = 2.7 nm), and a prototype core-shell (CS) QD, viz. (CdSe)₆₆/(ZnS)₁₁₉, (d = 2.8 nm), which is otherwise an arduous task on off-the-shelf contemporary hardware. MTA-assisted density functional method offers a reliable and rapid approach for initial steps of geometry optimization of medium and large nanoclusters. The geometrical features viz. surface reorganization through self-healing, selective localization of molecular orbitals, and size dependency of band gap are also retained by MTA. The present approach coupled with a dedicated high performance computer cluster thus has the potential of extending the limits of density functional framework to handle the nanoclusters larger than 3.5 nm (~few hundred atoms).</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144716666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Two-Step Hybrid Method for the Energetics of Individual Noncovalent Interactions in Molecular Crystals","authors":"Bharti Dehariya,&nbsp;Ayush Shivhare,&nbsp;Mini Bharati Ahirwar,&nbsp;Milind M. Deshmukh","doi":"10.1002/jcc.70190","DOIUrl":"https://doi.org/10.1002/jcc.70190","url":null,"abstract":"<div>\u0000 \u0000 <p>We present a two-step method for the direct estimation of the energy of individual non-covalent interactions (NCIs) such as hydrogen bond (HB), CH…π or π…π interactions in any given molecular crystal. The first step of this method is to calculate the energy of a NCI by a molecular tailoring approach based (MTA-based) method utilizing a sufficiently large molecular crystal structure. This calculation is performed at the low Hartree–Fock (HF) level. In the next step, the energy of the same referenced NCI is evaluated by the MTA-based method employing a suitable monomeric or dimeric species. This calculation is usually performed at both the high (B3LYP, MP2 or CCSD(T)) and low (HF) levels. Note that the NCI energies in monomeric or dimeric species are significantly different from those in the actual crystal. The difference in the energy calculated in the second step at high and low levels is added to the energy of this NCI calculated (at HF level) in the first step employing a large molecular crystal. The energies of NCIs calculated by this two-step method are compared with their actual crystal counterparts. For this purpose, molecular crystals of L-Histidine (LH), nitromalonamide (NMA) and salicylic acid (SA) are chosen as test cases. It is found that the proposed two-step method provides very accurate energy of individual NCIs in these molecular crystals. For instance, the estimated energies of NCIs by the proposed two-step method are in excellent linear agreement with their actual crystal counterparts (<i>R</i>² = 0.9983). Furthermore, RMSD and standard deviation are 0.22 and 0.24 kcal/mol, respectively, with a mean and maximum absolute error being 0.15 and 0.51 kcal/mol, respectively. Importantly, the two-step method is computationally efficient and saves nearly 50% of computational time <i>vis-à-vis</i> its full calculation counterpart employing the actual molecular crystal.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heterogeneous Autoxidation of VOCs Promotes Light-Scattering of Atmospheric Mineral Particle: A DFT Study","authors":"Weina Zhang,&nbsp;Zhichao Fan,&nbsp;Yao Zhou,&nbsp;Kaixin Zhang","doi":"10.1002/jcc.70195","DOIUrl":"https://doi.org/10.1002/jcc.70195","url":null,"abstract":"<div>\u0000 \u0000 <p>Recently, the heterogeneous autoxidation of volatile organic compounds (VOCs) has been shown to alter the light-scattering property of atmospheric mineral particles. Here, we investigate how VOCs with different central atoms dictate autoxidation pathways and subsequent highly oxygenated molecules (HOMs) properties, ultimately influencing the complex refractive index of VOC-mineral particles via density functional theory (DFT) and quantitative structure–property relationship (QSPR) analysis. Using dimethylsulfide (DMS)/dimethylether (DME) as ether-type proxies and triethylamine (TEA)/trimethylphosphine (TMP) as alkane-type proxies, we reveal two distinct autoxidation paths: alkane-type VOCs undergo more O₂-addition steps due to their structural capacity for H-shift reactions, generating HOMs with higher oxidation states (OS), molar mass, and polarizability. These properties drive stepwise increases in the refractive index (<i>n</i>) for alkane-VOC-mineral particles, leading to stronger light-scattering ability compared to ether-type counterparts. Our results establish a direct link between VOCs' autoxidation mechanisms and optical properties, providing new insights into climate-relevant aerosol interactions.</p>\u0000 </div>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Population Analysis From Variational Chemical Partition of Molecular Position Space","authors":"Bernard Silvi,&nbsp;M. Esmaïl Alikhani","doi":"10.1002/jcc.70184","DOIUrl":"https://doi.org/10.1002/jcc.70184","url":null,"abstract":"<p>Two years ago, a partition was proposed in the position space of the charge distribution of atoms and molecules, relying on the optimization of the boundaries of space-filling non-overlapping localization regions. This is achieved with the help of global objective functions providing either a measure of the dispersion of numbers of electrons in each localization region or of the dependence of these numbers between them. The output of the method reproduces very well the expected chemical structures in terms of atomic shells, bonds, and lone pairs domains. This method, inspired by the data processing of experimental results, is by construction free of any approximation since it only requires as input the one and two-particle densities of probability. It is based on a strict definition of the concepts of chemical entity, i, e, a set of nuclei and of a given number of localized electrons, for which an electron count followed by a multivariate analysis is carried out. In its first version, the software was extremely inefficient, and its use was therefore limited to atoms and small molecular systems to keep the computational effort within reasonable limits. A significant improvement has been recently achieved, enabling calculations of molecules as large as polyaromatic hydrocarbons. In the present paper, we first discuss the philosophy of previous population schemes, then we describe the features of our new family of population analysis, and then report the results obtained on a rather large sample of molecules and complexes, including polyaromatic hydrocarbons, propellanes, transition metal carbonyl 1:1 complexes and hydrogen-bonded systems as well as reaction mechanisms.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 20","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70184","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144705626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}