Physical Chemistry Chemical Physics最新文献

{"title":"Insights into the oxygen evolution mechanism of transition metal-anchored holey graphyne.","authors":"K Simmy Joseph,Brahmananda Chakraborty,Shweta Dabhi","doi":"10.1039/d5cp02097b","DOIUrl":"https://doi.org/10.1039/d5cp02097b","url":null,"abstract":"Growing worldwide environmental concerns linked to the overuse of fossil fuels and rising energy demands are driving a thorough and comprehensive search for clean, sustainable sources of energy. Water electrolysis has recently become a highly appealing method for achieving optimal energy conversion and storage. This study employs density functional theory to investigate the catalytic performance along with the electronic properties of pristine and adatom-doped transition metal (TMs = Sc, Pt, Co, Cr, and Au)-anchored holey graphyne (HGY). Among all considered candidates, Pt-doped HGY gives the best oxygen evolution reaction (OER) with the overpotential equivalent to 0.74 V. This catalyst is deemed optimal for further exploration of the OER mechanism. Through molecular dynamics (MD) simulations, the structural along with thermal stability of Pt@HGY has been confirmed. The convincing results motivate the use of Pt-anchored HGY as an efficient OER mechanism catalyst.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194633","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":"Planarity-Induced Enhancement of Excited-State Proton Transfer and Near-Infrared Emission in Conjugated N,N-Dimethylamino Cyclic Chalcone Derivatives: A Combined Photophysical and Theoretical Investigation","authors":"Balqees S. Al-Saadi, Ahmed H. Ismail, Younis Baqi, John Husband, Osama K. Abou-Zied","doi":"10.1039/d5cp03318g","DOIUrl":"https://doi.org/10.1039/d5cp03318g","url":null,"abstract":"The excited-state dynamics of chalcone-based chromophores are strongly influenced by molecular conformation, electronic delocalization, and solvation. In this work, we investigate the steady-state and ultrafast photophysics of a newly synthesized indanone-bridged chalcone derivative, (E)-2-(4-(dimethylamino)benzylidene)-7-hydroxy-2,3-dihydro-1H-inden-1-one (DHCF), to assess the role of conformational planarity in excited-state intramolecular proton transfer (ESIPT). Incorporation of the rigid, planar indan framework suppresses torsional motion around the phenyl ring and promotes efficient ESIPT, evidenced by additional red-shifted absorption and emission bands assigned to the tautomeric form. To validate this mechanism, we synthesized the corresponding hydroxyl-free analogue, (E)-2-(4-(dimethylamino)benzylidene)-2,3-dihydro-1H-inden-1-one (DCF). The absorption and fluorescence characteristics of DCF closely match those of the locally excited (LE) state of DHCF. Transient absorption spectroscopy of DHCF reveals tautomer formation on a ~3 ps timescale, coinciding with the rise of the tautomer's stimulated emission band, which subsequently decays within 48-108 ps depending on solvent. Direct comparison with DCF demonstrates that tautomer formation accelerates the LE relaxation, reducing its lifetime from 156 ps to 55 ps in acetonitrile and from 314 ps to 56 ps in dioxane. Complementary DFT and TD-DFT calculations provide insights into the potential energy surfaces and tautomerization pathways. These findings elucidate mechanistic understanding of structure-property relationships in ESIPT-active systems and provide guiding principles for the rational design of organic fluorophores for photonic and optoelectronic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"24 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194935","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":"Predicting Pesticide Vapour Pressures: The Power of Functional Groups","authors":"Mark Heezen, Manuel Alcami, Clemens Rauer, Freija De Vleeschouwer","doi":"10.1039/d5cp01965f","DOIUrl":"https://doi.org/10.1039/d5cp01965f","url":null,"abstract":"Explainable machine learning can aid in deriving chemical rules which in combination with inverse molecular design methods can support humans to optimise classes of molecules such as pesticides. This study demonstrates that pesticide vapour pressures can be predicted (77.1% within one order of magnitude) using kernel ridge regression on quantum chemical molecular properties but the model lacks interpretability. However, insights (via Shapley additive explanations) can be gained when a framework of functional groups is employed instead. A functional group-based model (66.7%withinoneorderofmagnitude)revealsthataromatic compounds, sulfonic acid derivatives, and carboxylic acid derivatives influence the vapour pressure the most. SHAP value trends indicate a linear relationship between reduced vapour pressure and the frequency of functional groups. A provided list of functional group contributions enables molecular modifications to optimise pesticide vapour pressures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"103 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194993","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":"Reaction Mechanism of Intramolecular C-C Coupling Catalyzed by the Non-heme Deoxypodophyllotoxin Synthase","authors":"Xue Zhang, Yongjun Liu","doi":"10.1039/d5cp02532j","DOIUrl":"https://doi.org/10.1039/d5cp02532j","url":null,"abstract":"Deoxypodophyllotoxin synthase (DPS) is a non-heme dioxygenase from Sinopodophyllum hexandrum that catalyzes the intramolecular C-C coupling reaction between the aromatic ring and the methylene group in the synthesis of the antitumor natural product podophyllotoxin. Three possible pathways for the C-C coupling reaction have been previously proposed, however, the reaction derails still remain unclear. In this work, we constructed computational models and performed QM/MM calculations to clarify the DPS-catalyzed intramolecular C-C bond formation mechanism. Our calculation results revealed that the C-C coupling reaction follows the radical electrophilic aromatic substitution (rEAS) mechanism rather than the electrophilic aromatic substitution (EAS) mechanism. The highly reactive species Fe(IV)=O first region-selectively abstracts a hydrogen atom from the C7ʹ (methylene) of substrate to trigger the coupling reaction. In addition, the typical OH rebound reaction is effectively blocked by the ligand exchange reaction within the iron center. The proton coupled electron transfer (PCET) between the substrate and the iron center further promotes the re-aromatization reaction of the intermediate. Based on the above results, we proposed that the non-heme-catalyzed coupling reaction between aromatic ring and methylene group should meet two basic conditions. First, the substrate should be well positioned to facilitate the hydrogen atom abstraction. Second, the special coordination center can effectively inhibit the OH rebound reaction. Third, the PCET between from the substrate to the iron center can greatly promote the re-aromatization of C-C coupled intermediate. These results may provide useful information for further understanding biosynthesis of cyclized natural products catalyzed by the non-heme enzymes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188988","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":"Strong-field induced ionization and dissociation of cis- and trans-1,2-dichloroethylene: Cl+ and HCl+ fragments","authors":"Ephraim Anto, Rituparna Das, Vinitha Nimma, Madhusudhan P, Pranav Bhardwaj, Pooja Chandravanshi, Rajesh Kumar Kushawaha, Koushik Saha","doi":"10.1039/d5cp03038b","DOIUrl":"https://doi.org/10.1039/d5cp03038b","url":null,"abstract":"Strong-field induced ionization of polyatomic molecules using femtosecond laser pulses leads to complex fragmentation dynamics like bond-breaking, intramolecular proton migration, roaming, bond formation, and Coulomb explosion. In this work, we report the strong-field induced ionization and dissociation dynamics of cis- and trans- 1, 2-dichloroethylene (DCE) employing ion momentum spectroscopy with multi-ion coincidence detection of fragment ions. Two-body dissociation from doubly ionized molecular ion involving Cl<small>⁺</small> ejection <em>i.e.</em>, Cl<small>⁺</small> + C<small>₂</small>H<small>₂</small>Cl<small>⁺</small> channel and HCl<small>⁺</small> ejection <em>i.e.</em>, HCl<small>⁺</small> + C<small>₂</small>HCl<small>⁺</small> channel, are studied in detail as a function of laser pulse durations. A lower kinetic energy release (KER) is observed for cis-DCE as compared to trans-DCE for both fragmentation channels, which is attributed to the different conformation of the isomers. Two distinct peaks are observed in the KER spectra for both Cl<small>⁺</small> and HCl<small>⁺</small> ejection channels, indicating that two different excited states/distinct reaction pathways are involved in the dissociation process. Quantum chemical calculations reveal that the Cl<small>⁺</small> ejection channel follows three different pathways, one from direct C-Cl bond break-up, and the other two pathways are from intermediate states. On the other hand, HCl<small>⁺</small> formation is possible via two pathways with two intermediate states. Dissociation lifetimes of the parent ions are estimated from the angular distribution of fragments. A longer lifetime is observed for cis-DCE as compared to trans-DCE for both the fragmentation channels.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"27 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189413","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":"Vibrational energy landscapes and energy flow in GPCRs: Comparison between class A and class B GPCRs using all atom and coarse-grained models","authors":"Humanath Poudel, Pathick Halder Shaon, David J Wales, David M. Leitner","doi":"10.1039/d5cp02918j","DOIUrl":"https://doi.org/10.1039/d5cp02918j","url":null,"abstract":"We compare vibrational energy landscapes and dynamics of glucagon-like peptide 1 receptor (GLP-1R), a class B G-protein coupled receptor (GPCR), with corresponding properties of a class A GPCR studied previously. Energy flow in GLP-1R is computed by molecular dynamics (MD) simulations in active and inactive states using all atom (AA) and coarse-grained (CG) models. Based on the MD data, we construct and analyze the vibrational energy landscape of GLP-1R, focusing on the relative free energy of each residue and the minimum free energy barriers for energy transfer between them. We find that prolines and glycines, which contribute to GLP-1R plasticity and function, are bottlenecks to energy transport along the backbone, causing diversion of energy through alternative pathways via nearby noncovalent contacts. The probability distributions for the energy transfer time between numerous pairs of amino acids are computed, revealing pathways for energy transport that include noncovalent contacts connecting different helices. These distributions and mean energy transfer times are similar for the AA and CG models, validating the CG representation for future applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"100 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189417","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":"A DFT-based study of As2O3 adsorption using single and bimetallic atom-doped g-C3N4","authors":"Jialiang Sun, Xiantuo Chen, Shun Liu, Dapeng Wang, Min Li, Guangqian Luo, Hong Yao, Jiang Wu, Qizhen Liu","doi":"10.1039/d5cp02303c","DOIUrl":"https://doi.org/10.1039/d5cp02303c","url":null,"abstract":"Non-precious metal atom-doped g-C<small>₃</small>N<small>₄</small> is a promising adsorbent for arsenic removal from coal-fired flue gas, but the adsorption process and mechanisms are unclear. This work systematically investigates As<small>₂</small>O<small>₃</small> adsorption on single- and double-transition-metal-loaded g-C<small>₃</small>N<small>₄</small> using density functional theory, examining the adsorption location, structure, energy, and charge density. Calculations show that metal doping significantly improves As<small>₂</small>O<small>₃</small> adsorption capacity. Adsorption energy on M<small>₂</small>/g-C<small>₃</small>N<small>₄</small> (where M<small>₂</small> denotes a bimetallic atom) exceeds that on M/g-C<small>₃</small>N<small>₄</small> (where M denotes a monometallic atom) due to bimetallic atoms' synergistic and electronic effects. Co<small>₂</small> introduction has the most obvious effect, with an adsorption energy of −565.1 kJ mol<small>⁻¹</small>—4.36 and 2.25 times higher than that of pure g-C<small>₃</small>N<small>₄</small> and monoatomic Co doping, respectively. This indicates that bimetallic doping favors As<small>₂</small>O<small>₃</small> adsorption. Projected density of states and adsorption process analysis further verify the excellent performance of bimetallic-doped g-C<small>₃</small>N<small>₄</small>. This DFT study contributes to understanding the atomic-scale adsorption mechanism and aids in the rational design of high-performance adsorbents.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"2 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189419","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":"Understanding Contrasting S2→S1 Internal Conversion Rates in Boron-Dipyrromethene Derivatives via Multi-Configuration Time-Dependent Hartree Method","authors":"Neethu Anand, Munnyon Kim, Changmin Lee, Jinhyuk Ma, Taiha Joo","doi":"10.1039/d5cp02771c","DOIUrl":"https://doi.org/10.1039/d5cp02771c","url":null,"abstract":"Internal conversion (IC) dynamics from higher-lying to lower electronic states following photoexcitation are often described as ultrafast, occurring in much less than 1 ps. However, IC processes can exhibit a range of time scales, depending critically on the energetic landscape of excited-state manifolds and the strength of vibronic couplings that drive nonadiabatic transitions. These dynamics play a fundamental role in most photochemical and photophysical applications. A previous time-resolved fluorescence study revealed that two structurally analogous boron-dipyrromethene (BODIPY) molecules, PM650 and PM597, exhibit markedly different IC rates, despite both undergoing ultrafast IC in &lt;100 fs from the S3/S2 to the S1 state. Nuclear wave packets persisting in the S1 state after the IC were also observed by time-resolved fluorescence. To elucidate the origin of these divergent IC rates and the nature of vibronic interactions among excited states, we performed theoretical simulations using the multiconfiguration time-dependent Hartree (MCTDH) method. Our results reveal nonadiabatic decay pathways mediated by vibronically coupled S1, S2, and S3 potential energy surfaces, with multiple conical intersections (CIs) enabling the IC processes. The IC rates obtained from the MCTDH simulations are in good agreement with the experimental observations, including the contrasting rates for PM650 and PM597. Importantly, the proximity of CIs to the Franck–Condon region was found to significantly influence IC efficiency. As more vibrational modes were incorporated into the model, a consistent acceleration of the IC dynamics was observed, underscoring the role of multimode effects in nonadiabatic transitions through CIs. Additionally, coherent vibrational spectra of the S1 state, generated from nuclear densities computed via MCTDH following excitation to higher states, were found to match experimental results closely, further supporting the conclusions of this study. Overall, these findings advance our understanding of the intricate excited-state dynamics and highlight the critical role of vibronic coupling and CIs in ultrafast IC.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"94 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189060","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":"Proton transfer across four-member hydrogen bonded network prefers over six-member hydrogen bonded network: Lactim-Lactam vs Imine-Amine photoisomerization","authors":"Souvik Santra, Rintu Mondal, Nikhil Guchhait","doi":"10.1039/d5cp02420j","DOIUrl":"https://doi.org/10.1039/d5cp02420j","url":null,"abstract":"In this article, lactim-lactam vs imine-amine photoisomerization in two molecules namely 3-(benzo[d]thiazol-2-yl)pyridin-2-ol (BTPO) and 3-(1H-benzo[d]imidazol-2-yl)pyridin-2-ol (BIPO) has been studied using steady-state and time-resolved spectroscopic methods. The solved structure obtained from single crystal XRD data, revealed the lactam form of these molecule as the most stable structure which was further supported by theoretical calculation using Density Functional Theory (DFT) method. Experimental results are in favour of preferential occurrence of lactim-lactam tautomerism over imine-amine tautomerism. From structural view point, as evident from the crystallographic structure, the proton acceptor nitrogen atom involving imine-amine tautomerism is oriented opposite to the proton donor oxygen atom hence structural inhibition plays a major role in the determining the preferentiality of the two competitive proton transfer pathways. The potential energy curves for the two different proton transfer paths in the ground and excited state were computed using Density functional theory (DFT) at B3LYP/6-311++g(d,p) level to corroborate with experimental findings.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188991","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":"Diffraction of fast heavy noble gas atoms, Ar, Kr and Xe on a LiF(001) surface, changing the tip of a ‘perfect’ AFM","authors":"Maxime Debiossac, Peng Pan, Carina Kanitz, Philippe Roncin","doi":"10.1039/d5cp01817j","DOIUrl":"https://doi.org/10.1039/d5cp01817j","url":null,"abstract":"We investigate experimentally the diffraction of fast atoms of noble gas on a LiF(001) crystal oriented along the [100] and [110] directions. All exhibit some quantum features but wavelengths are so short that these effects are qualitatively described by semi-classical models. With increasing mass and energy, the scattering profiles show an increasing number of diffraction peaks forming an increasing number of supernumerary rainbow peaks but progressively weakening in contrast with the innermost peaks correspond to individual quasi-specular Bragg peaks disappearing first. Along the [100] direction, all observed azimuthal profiles are well described by Bessel functions allowing a simple semi-quantitative analysis. After removing the contributions of the attractive forces, we show how the surface corrugation amplitude and its variation strongly depend on the probing atom. These data should be compared with those accessible with an atomic force microscope (AFM).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145188987","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}