Structural Chemistry最新文献

{"title":"Yury T. Struchkov centennial: a life for crystallography","authors":"Istvan Hargittai","doi":"10.1007/s11224-026-02745-1","DOIUrl":"10.1007/s11224-026-02745-1","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 5","pages":"2945 - 2947"},"PeriodicalIF":2.3,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148950441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparative analysis of molecular conformer contributions to the Localization–Delocalization matrix and associated metrics","authors":"Pomila,&nbsp;Robert Mawhinney","doi":"10.1007/s11224-026-02752-2","DOIUrl":"10.1007/s11224-026-02752-2","url":null,"abstract":"<div><p>We quantify electronic similarity across conformers of eight sulfur-containing systems using localization–delocalization matrices (LDMs) from Quantum Theory of Atoms in Molecule (QTAIM<i>)</i> and the Frobenius distance (FD) as a matrix-based metric. After conformer sampling and <span>(:omega:)</span>B97X-D/6-311G(2d, p) optimization, we analyzed 630 unique conformers (allyl mercaptan, 2-propenesulfenic acid, diallyl monosulfide, diallyl disulfide, diallyl trisulfide, allicin, and the <span>(:E/Z)</span> isomers of ajoene). Conformers were grouped according to their QTAIM molecular graph classification into acyclic, ring critical point (RCP), or cage critical point (CCP) types. Pairwise FD_R values within and across topological classes are generally small (typically ≤ 0.10–0.15), indicating that electron density is largely preserved despite substantial conformational flexibility and distinct topological features, including ring and cage critical points. Analysis of bond critical points associated with these features reveals low electron density and negligible delocalization, consistent with weak intramolecular interactions that modify topology without inducing significant electronic redistribution. Boltzmann-weighted averaging at 298 K yields ensemble-averaged LDMs that closely resemble those of the lowest-energy conformers, and equivalent trends are obtained at physiological temperature (≈ 300 K), confirming the robustness of the electronic similarity under thermally accessible conditions. A gradual increase in mean FD_R from R1 (≈ 0.07) to R4 (≈ 0.11) reflects modest electronic reorganization with increasing regime index rather than abrupt changes. Overall, these results demonstrate that pronounced topological differences do not necessarily imply significant electronic reorganization and establish LDM-based descriptors (FD, FD_W, N_loc, and N_deloc) as compact and robust measures of conformer similarity, clarifying when single-conformer approximations are adequate and providing a foundation for future extensions to protein-binding relevant conformational landscapes.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1739 - 1762"},"PeriodicalIF":2.3,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613834","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational tailoring of polycyclic aromatic hydrocarbons by N and B atoms: insights into NLO response, solvent effects and photovoltaic properties","authors":"Shamsa Bibi,&nbsp;Uswa Mustafa,&nbsp;Shabbir Muhammad,&nbsp;Iqra Kaifi,&nbsp;Shafiq UrRehman,&nbsp;Saleh S. Alarfaji,&nbsp;Abdullah G. Al-Sehemi,&nbsp;Aijaz Rasool Chaudhry","doi":"10.1007/s11224-026-02739-z","DOIUrl":"10.1007/s11224-026-02739-z","url":null,"abstract":"<div>\u0000 \u0000 <p>Polyaromatic Hydrocarbons (PAHs) are a versatile class of organic compounds mainly studied for their unique electronic and tunable optical characteristics and applications. This study presents a comparative quantum computational exploration of novel boron and nitrogen-doped PAH derivatives. Specifically, we have designed ten unique structures, designated as BPAH-1 to BPAH-5 and NPAH-1 to NPAH-5, incorporating boron and nitrogen substitutions. Using DFT and TD-DFT methods, BPAH-3 and NPAH-3 consistently exhibit enhanced linear isotropic (α_iso) and anisotropic (α_aniso) polarizabilities and demonstrate enhanced &lt; γ &gt; values. In particular, the α_iso values for BPAH-3 and NPAH-3 are 66.08 × 10⁻²⁴ esu and 64.25 × 10⁻²⁴ esu, respectively. Impressively, these systems achieved &lt; γ &gt; amplitudes as high as 206 × 10⁻³⁶ esu (BPAH-3) and 144.4 × 10⁻³⁶ esu (NPAH-3), surpassing the benchmark NLO molecule, <i>para</i>-nitroaniline (<i>p</i>-NA), approximately 28.61 and 20.06 times, respectively, at the same theoretical level. Solvent effects using the PCM model reveal further enhancements; the &lt; γ &gt; value of BPAH-3 increases by approximately 2.94 times in chloroform and 4.30 times in methanol, highlighting its robust performance under different solvent conditions. TD-DFT calculations further confirmed the highest NLO response of BPAH-3, showing the lowest value of transition energy 2.694 eV. BPAH-3 and NPAH-3 systems also show excellent light-harvesting efficiencies of 0.641 eV and 0.657 eV, respectively. Our findings identify the significant potential of these novel derivatives, with the BPAH-3 compound standing out, for advanced optoelectronic applications, including OLED displays, NLO devices for photonics, high-speed optical communication, and next-generation solar cells.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"2047 - 2071"},"PeriodicalIF":2.3,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Experimental and computational study of the crystal packing of isoelectronic 4,11-diaza[5]helicene and 4,7,8,11-tetraaza[5]helicene","authors":"Giovanni Macetti,&nbsp;Francesca Fontana,&nbsp;Monica Panigati,&nbsp;Simona Rizzo,&nbsp;Margherita Vacchini,&nbsp;Luca Sironi,&nbsp;Leonardo Lo Presti","doi":"10.1007/s11224-026-02724-6","DOIUrl":"10.1007/s11224-026-02724-6","url":null,"abstract":"<div><p>The crystal structures of isoelectronic 4,11-diaza[5]helicene (DNH) and 4,7,8,11-tetraaza[5]helicene (TNH) are accurately determined at room temperature by single crystal X-ray diffraction. Analysis of crystal packing with computational chemistry tools, including the evaluation of intermolecular and cohesive energies with force field and charge density (PIXEL) methods, highlights the effect of skeletal replacement of two aromatic C-H with nitrogen atoms. Both crystals are centrosymmetric racemates, with asymmetric units (ASUs) exploiting the same conformation. The ASU of TNH bears two symmetry-independent enantiomers, and the different settings of symmetry operators mirror in different packing motifs with respect to DNH. Both structures exhibit columnar stacking arrangements, which differ in their mutual orientation, distance and strength. Stacking interactions are more frequent and stronger in the tetraaza compound, owing to the greater intrinsic polarization of its ground-state electron density that favors antiparallel arrangements of neighboring molecular dipole moments. Finally, the possible existence of thermodynamically stable chiral forms of the title compounds is investigated by symmetry-constrained Monte Carlo (SC-MC) calculations.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1177 - 1190"},"PeriodicalIF":2.2,"publicationDate":"2026-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-026-02724-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147938275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantum chemical exploration of central core modification and its influence on NLO properties, solvent effects and charge transfer dynamics","authors":"Muhammad Ali,&nbsp;Sana Fatima,&nbsp;Muhammad Aslam,&nbsp;Mehwish Haq Nawaz,&nbsp;Azhar Iqbal,&nbsp;Abdul Razzaq","doi":"10.1007/s11224-026-02737-1","DOIUrl":"10.1007/s11224-026-02737-1","url":null,"abstract":"<div><p>The development of organic materials with strong nonlinear optical (NLO) response is essential for advanced optoelectronic applications. In this study, a series of BN-based chromophores (BN-1 to BN-9) is designed by integrating triphenylamine (TPA) and triphenylborane (TPB) units through aliphatic and heterocyclic linkers, and their NLO properties are systematically investigated using density functional theory (DFT). Among the studied NLO systems, BN-9 exhibits the most pronounced third-order NLO Polarizability, with a &lt; γ &gt; value of 810 × 10^− 36 esu, exceeding ~ 109.5 times that of <i>para</i>-nitroaniline. This robust NLO response of BN-9 is attributed to enhanced intramolecular charge transfer (ICT) and reduced crucial orbital energy gap. The influence of Polarizable Continuum Model (PCM) and Conductor-like Screening Model (COSMO) solvation models on α_aniso and &lt; γ &gt; for three selected systems (BN-1, BN-6, and BN-9) is also evaluated. Both models show a steady increase in &lt; γ &gt; as compared to the gas phase, and a more intense increase in polar solvents because of dielectric stabilization of charge-transfer states. Even though COSMO provides a marginally higher result in comparison with PCM, the trends of both solvation models indicate the solvent-dependent NLO response of the designated systems. The frequency-dependent NLO response of BN-9 is found to be 1161.1 × 10^− 36 esu at 1907 nm under EFISHG process, emphasizing the utility of the designated systems under a wide range of laser wavelengths. Additionally, TD-DFT analysis shows the lowest transition energy of 2.915 eV for BN-9, supporting the robust NLO response. The integration of aliphatic and heterocyclic cores with engineered TPA-TPB scaffolds demonstrates a versatile molecular framework, paving the way for advanced functional materials in NLO applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"2073 - 2093"},"PeriodicalIF":2.3,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular dynamics simulations of the mechanically induced crystallization of carbamazepine’s trigonal polymorph, CBZ(II)","authors":"Joseph Kioseoglou,&nbsp;Elena Boldyreva,&nbsp;Kyriakos Kachrimanis","doi":"10.1007/s11224-026-02731-7","DOIUrl":"10.1007/s11224-026-02731-7","url":null,"abstract":"<div><p>The present study investigates the mechanism by which the thermodynamically stable form of carbamazepine, CBZ(III), transforms to the trigonal polymorph, CBZ(II), during ball milling in the presence of palmitic acid. Crystal-structure and lattice-energy analyses were performed, and molecular dynamics (MD) simulations provided insight into crystal-surface and molecular-level phenomena underpinning the phase transformation. The PIXEL formalism and the all-atom Coulomb–London–Pauli method reproduced the experimentally observed stability order between CBZ(III) and CBZ(II). MD indicates limited miscibility between CBZ and palmitic acid—both at crystal surfaces and in the melt. The transformation proceeds via surface fluidization of CBZ(III) and hydrophobic-interaction–driven aggregation of CBZ around palmitic-acid alkyl chains. MD of palmitic-acid inclusion in CBZ(II) channels, together with pore analyses, suggests that stable inclusion would require lattice dilation. Trajectory inspection further shows frequent guest–wall repulsive contacts that can expel palmitic acid from the voids. Further work is warranted to test whether the transformation mechanism proposed for the polymorphic transformation of CBZ(III)→CBZ(II) generalizes to other mechanically induced solid-state transformations.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1119 - 1132"},"PeriodicalIF":2.2,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-026-02731-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147937919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pseudoatomic charge constraints governing the distribution of the partial charge densities. The atoms and force-field pseudoatoms in the hexagonal and cubic boron nitride crystals","authors":"Sergey V. Kartashov,&nbsp;Robert R. Fayzullin","doi":"10.1007/s11224-025-02636-x","DOIUrl":"10.1007/s11224-025-02636-x","url":null,"abstract":"<div><p>This work presents a physically consistent framework in which, in accordance with Gauss’s flux theorem, the partial charge densities are interpreted as source terms, each generating the corresponding conservative electronic force field. A new population constraint is formulated for the pseudoatomic basins <span>(Omega_{P})</span> defined in the total kinetic force field <span>(mathbf{F}_{k}(mathbf{r}))</span>: in any many-electron multinuclear system, the integral populations of the von Weizsäcker and Pauli charge densities within the same closed <span>(Omega_{P})</span> basin exactly cancel each other. Under equilibrium conditions, this constraint can be combined with the previously established constraint for the equivalent pseudoatomic basins <span>(Omega_{P})</span> defined in the total static force field <span>(mathcal{F}(mathbf{r}))</span>. This yields a comprehensive and unified condition that governs both local charge (re)distribution and force-field pseudoatomic charges and simultaneously reflects the balance between kinetic and static effects in the charge organization of matter. This framework is further applied to the hexagonal and cubic boron nitride (BN) crystals. Their electronic structures are analyzed in terms of the superposition of the chemically bonded atoms identified in the electron density gradient <span>(nabla rho(mathbf{r}))</span>, the pseudoatoms defined in the electrostatic force field <span>(mathbf{F}_{text{es}}(mathbf{r}))</span>, and those defined in the local-density-approximated force field <span>(mathbf{F}_{k}(mathbf{r}))</span> or <span>(mathcal{F}(mathbf{r}))</span>, whose electron populations are subject to the corresponding charge constraints. This perspective elucidates both the interatomic electron transfer and the responsive sharing of the transferred density. The quantum chemical responses associated with the latter are nearly spatially complete within the graphene-like layers in hexagonal BN but are markedly attenuated between them. This contrast is further supported by the distribution of the local-density-approximated exchange charge density <span>(q_x(mathbf{r}))</span>, which reveals a pronounced condensation of electron-pair density in the internuclear binding regions within the layers and a significant depletion in the binding regions between the layers. Concurrently, the B–N bond in cubic BN exhibits a comparably complete quantum chemical response. The differences in the spatial superposition patterns of the vector fields account for the distinct mechanical properties of the two polymorphs, despite the similar atomic and pseudoatomic charges within them. Additionally, in a closely related context, nonpolar interatomic interactions in graphite and diamond are briefly discussed.\u0000</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1919 - 1932"},"PeriodicalIF":2.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pseudoatomic charge constraints and force-field flux relations governing local charge redistribution in electron–nuclear systems. An electronic-force-based insight into interatomic binding in diborane","authors":"Sergey V. Kartashov,&nbsp;Robert R. Fayzullin","doi":"10.1007/s11224-025-02613-4","DOIUrl":"10.1007/s11224-025-02613-4","url":null,"abstract":"&lt;div&gt;&lt;p&gt;Herein, the charge constraints for the force-field basins in molecular systems are formulated together with the governing relations for the fluxes of the electronic force fields through the boundaries of the atomic and force-field basins, &lt;span&gt;({Omega }_{S})&lt;/span&gt; and &lt;span&gt;({Omega }_{P})&lt;/span&gt;, defined by the electron density gradient &lt;span&gt;(nabla rho(mathbf{r}))&lt;/span&gt; and the conservative total static force field &lt;span&gt;(mathcal{F}(mathbf{r}))&lt;/span&gt;, respectively. A chemically meaningful interpretation of the electron occupancy of the &lt;span&gt;({Omega }_{P})&lt;/span&gt; basins is provided in terms of the exchange charge. It is demonstrated that the emergence of the negative exchange charge density, &lt;span&gt;({q}_{x}(mathbf{r})=nabla cdot {mathbf{F}}_{x}(mathbf{r})/(4pi))&lt;/span&gt;, characterizes the “exclusion” effect arising from the condensation of fermionic electrons into electron pairs. Furthermore, the electrostatic-field and total-static-field fluxes through the interatomic surface are interpreted to be induced by the difference in actual electronegativity between the chemically bonded atoms. This study advances an exploration of the subatomic structure of the diborane molecule by employing the above formulations in conjunction with recently developed exchange-force-derived chemical structure descriptors. It is revealed that the hydrogen exchange-force-field basins &lt;span&gt;({Omega }_{X})&lt;/span&gt;—each containing a hydrogen nucleus yet governed by a nonnuclear attractor—encompass the internuclear binding regions associated with the highly polar B–H and B–&lt;span&gt;(mu)&lt;/span&gt;-H covalent bonds. When considering the conservative exchange force field &lt;span&gt;(mathbf{F}_{x}(mathbf{r}))&lt;/span&gt;, both the nonnuclear attractors of the &lt;span&gt;({Omega }_{X})&lt;/span&gt; basins of the bridging hydrogen (&lt;span&gt;(mu)&lt;/span&gt;-H) sites are directly connected by two gradient trajectories, which originate at the line-type saddle equilibrium point situated at the geometric center of the B&lt;sub&gt;2&lt;/sub&gt;&lt;span&gt;(mu)&lt;/span&gt;-H&lt;sub&gt;2&lt;/sub&gt; rhombus. Notably, nearly all of negative &lt;span&gt;(q_x(mathbf{r}))&lt;/span&gt;, within the valence shell is confined to the hydrogen &lt;span&gt;({Omega }_{X})&lt;/span&gt; and &lt;span&gt;({Omega }_{S})&lt;/span&gt; basins. Specifically, &lt;span&gt;(q_x(mathbf{r}))&lt;/span&gt; assumes a dumbbell-shaped negative distribution that spans the &lt;span&gt;(mu)&lt;/span&gt;-H nuclei, thereby indicating the condensation of electron-pair density among them. By contrast, the hydrogen &lt;span&gt;({Omega }_{P})&lt;/span&gt; basins avoid capturing an excessive portion of negatively valued &lt;span&gt;(q_x(mathbf{r}))&lt;/span&gt; in accordance with the corresponding charge constraint imposed on &lt;span&gt;({Omega }_{P})&lt;/span&gt;. Furthermore, the negative scalar component of &lt;span&gt;(mathbf{F}_{x}(mathbf{r}))&lt;/span&gt;, contributing to &lt;span&gt;(mathcal{F}(mathbf{r}))&lt;/span&gt;, coupled with the positive scalar component of &lt;span&gt;(mathbf{F}_{x}(mathbf{r}))&lt;/span&gt;, contributing to the interelectron interaction force &lt;span&gt;(mathbf{F}_{text{ee}}(mathbf{r}))","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1933 - 1949"},"PeriodicalIF":2.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148613068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Substituent effects on benzene: A detailed analysis of ortho, meta and para positions","authors":"Mohanasudha Kanagavel,&nbsp;Karthika Mylsamy","doi":"10.1007/s11224-025-02704-2","DOIUrl":"10.1007/s11224-025-02704-2","url":null,"abstract":"<div>\u0000 \u0000 <p>Ab initio method was employed to investigate the effect of substituents in the ortho, meta and para positions of the benzene ring using def2-TZVPP basis set. The substituents energetically make σ-bond with the carbon atom in the hexagonal ring. Relative energy, dipole moment and chemical shift have been calculated using MP2/def2-TZVPP level of theory. Higher dipole moment is observed in ortho-substituted isomers due to steric and electronic effects. NMR analysis reveals the shielding and deshielding of carbon atoms in the hexagonal ring with respect to the substituents. Further, Frontier molecular orbital analysis and electrostatic potential map (ESP) were plotted to analyze the molecular properties. This study provides adequate knowledge for understanding the structural and electronic behavior of disubstituted benzene, with implications in chemical and material sciences.</p>\u0000 </div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 3","pages":"1577 - 1588"},"PeriodicalIF":2.2,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147937739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Towards an absolute aromaticity scale from localization-delocalization matrix approach","authors":"Julien Pilmé,&nbsp;Riccardo Spezia","doi":"10.1007/s11224-025-02707-z","DOIUrl":"10.1007/s11224-025-02707-z","url":null,"abstract":"<div><p>Aromaticity is one of the most emblematic concepts in chemistry, with benzene as its archetypal molecule, whose structural features are found in a wide variety of compounds. However, the definition of an unequivocal aromaticity scale is still an active field. Here we show how, by comparing Localization-Delocalization Matrix (LDM) descriptor obtained from electronic structure calculations with formal LDM systems, it is possible to quantify the aromaticity of 6-membered ring systems, both as parts of more extended networks and as substituted benzenes. In particular, we set reference systems based on the ideal population scheme of a fully delocalized system as well as of a more general electron-gas system. Results show that, using the Frobenius distance, it is possible to obtain values in agreement with simple aromaticity measures across these two series, indicating that the use of a reference electron-gas structure is feasible. This paves the way for considering aromaticity not only as a local property of benzene moieties in molecules but also as a property of entire systems.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"37 4","pages":"1775 - 1790"},"PeriodicalIF":2.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148614788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}