Physical Chemistry Chemical Physics最新文献

{"title":"The Critical Role of Fe 3d-N 2p Orbital Hybridization in Ammonia Decomposition on graphene-supported Fe6Nx Clusters: A DFT study","authors":"kaixun yi, Fengyun Ding, Habibullah ., Wanglai Cen, Tao Gao","doi":"10.1039/d4cp04613g","DOIUrl":"https://doi.org/10.1039/d4cp04613g","url":null,"abstract":"Ammonia (NH3) is a promising carbon-free hydrogen carrier, but lowering the temperature required for its catalytic decomposition to produce H2 remains a challenge. A main obstacle is the strong adsorption of nitrogen (N) on the active sites, which can remain on the catalyst's surface and lead to poisoning. Using first-principles calculations, we investigate the effects of N accumulation on the Fe6 cluster during NH3 decomposition and aim to develop strategies to mitigate N poisoning. Graphene-supported Fe6 cluster mitigate N poisoning by reducing Fe-N interaction strength, thereby improving NH3 decomposition efficiency. The energy barriers of the graphene-supported Fe6Nx (x=1, 2) clusters’ rate-limiting step has been reduced below 2 eV, compared to those calculated for the pure Fe6 cluster (2.08 eV) and the graphene-supported Fe6 cluster (2.53 eV). The rate-limiting step involves the Fe 3d-N 2p hybridization, during which an adsorbed N atom migrates across the Fe-Fe bond and combines with another N atom to form N2. This study provides new insights into the potential application of graphene-supported metal catalysts for NH3 decomposition.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675169","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":"Accurate Prediction of Ionic Liquid Density-of-States from Low-Cost Calculations","authors":"Richard Fogarty, Richard Paul Matthews, Patricia A. Hunt, Kevin R. J. Lovelock","doi":"10.1039/d5cp00214a","DOIUrl":"https://doi.org/10.1039/d5cp00214a","url":null,"abstract":"The electronic structure of ionic liquids (ILs) is a key factor in their chemical reactivity. Experimental techniques provide insight into IL electronic structure (<em>e.g.</em> X-ray photoelectron spectroscopy, XPS), but are impractical for screening large numbers of potential ILs. Computational screening offers an alternative approach, but current ab initio calculation methods (ion-pairs or large calculations with periodic boundaries) are not suitable for screening. We establish that a simple and computationally low-cost method, lone-ions evaluated at the B3LYP-D3(BJ)/6-311+G(d,p) level employing a generalised solvation model SMD (Solvation Model based on Density), captures IL liquid-phase density-of-states (DoS) with good accuracy by validating against XPS data for a wide range of ILs. The additivity of the results from individual lone-ion calculations provides a significant advantage, enabling predictions of the DoS for a large number of ILs and delivering a significant step towards the computational screening of ILs for many applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666590","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":"Development of a chemical code applicable to ions based on the PHITS code for efficient and visual radiolysis simulations","authors":"Yusuke Matsuya, Yuji Yoshii, Tamon Kusumoto, Tatsuhiko Ogawa, Seiki Ohnishi, Yuho Hirata, Tatsuhiko Sato, Takeshi Kai","doi":"10.1039/d4cp04216f","DOIUrl":"https://doi.org/10.1039/d4cp04216f","url":null,"abstract":"Water radiolysis plays an important role in elucidating radiation-induced biological effects such as early DNA damage induction, chromosome aberrations, and carcinogenesis. Several Monte Carlo simulation codes for water radiolysis, commonly referred to as chemical simulation codes, have been developed worldwide. However, these codes typically require substantial computational time to calculate the time-dependent <em>G</em> values of water radiolysis species (<em>e.g.</em>, ˙OH, e<small>⁻</small><small>_aq</small>, H<small>₂</small>, and H<small>₂</small>O<small>₂</small>), and their application is often limited to specific ion beam types. In the Particle and Heavy Ion Transport code System (PHITS), the track-structure mode that allows the simulation of each atomic interaction in liquid water for any charged particles and the subsequent chemical code (named PHITS-Chem code) dedicated to electrons was developed previously. In this study, we developed the PHITS-Chem code to support a broader range of ion beam species. To reduce computational time, we introduced new features including a space partitioning method to increase the detection efficiency of reactions between chemical species and a radical scavenger model that reduces the lifetime of OH radicals. We benchmarked the updated PHITS-Chem code by comparing its predicted time-dependent <em>G</em> values for protons, α particles, and carbon ions with those reported in the literature (<em>i.e.</em>, other simulation and measured data). The inclusion of a space partitioning method and the modified OH radical scavenger model reduced the time required by the PHITS-Chem code to calculate <em>G</em> values (by approximately 28-fold during radiolysis simulations under 1-MeV electron exposure) while maintaining calculation accuracy. A key advantage of the PHITS-Chem code is the four-dimensional visualization capability, integrated with PHITS′ native visualization software, PHIG-3D. Considering the ability of the PHITS-Chem code to handle OH radical scavengers (<em>i.e.</em>, tris(hydroxymethyl)aminomethane and dimethyl sulfoxide), it is anticipated to offer precise and intuitive insights into the radiation-induced biological effects of chemical species in ion-beam radiotherapy.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666595","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":"Stereodynamical control of resonances in the Cl + H2 (v = 1, j = 1) → HCl + H reaction","authors":"Xiaoxi Xu, Bayaer Buren, Maodu Chen","doi":"10.1039/d4cp04733h","DOIUrl":"https://doi.org/10.1039/d4cp04733h","url":null,"abstract":"The stereodynamical control of resonance profoundly influences the outcomes of molecular collisions. Here, we perform time-dependent wave packet calculations for the Cl + H<small>₂</small> (<em>v</em> = 1, <em>j</em> = 1) → HCl + H reaction to investigate how stereodynamical control influences reaction resonances. The results of the dynamical calculations indicate that the backward scattering differential cross section of the HCl (<em>v</em>′ = 2) product exhibits two pronounced peaks at collision energies of ∼0.4 eV and ∼0.5 eV. Analysis confirms that these characteristic peaks are attributable to reaction resonances. This work explores the impact of different alignment angles of the H<small>₂</small> reactant molecule on these two reaction resonances. It is found that the parallel alignment of the H<small>₂</small> molecule markedly amplifies the intensity of the resonance peaks, while the perpendicular alignment results in a notable suppression of these features. Furthermore, the alignment angle of the reactants significantly influences the scattering direction of the products. Products at the energies of resonances from the head-on collision tend to scatter in the backward direction. In contrast, those from the side-on collision are more likely to scatter forward and sideways.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"46 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666442","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":"First-principles analysis of the photocurrent in a monolayer α-selenium p–n junction optoelectronic device","authors":"Yuqian Wang, Xiaoyong Xiong, Shibo Fang, Hong Li, Zhulin Weng, Dahua Ren, Qiang Li","doi":"10.1039/d4cp04763j","DOIUrl":"https://doi.org/10.1039/d4cp04763j","url":null,"abstract":"Two-dimensional monoelemental materials have emerged as promising candidates for use in the development of next-generation optoelectronic devices. In this work, we investigate the photovoltaic effect of monolayer (ML) α-selenium p–n junctions by using <em>ab initio</em> quantum transport simulations. Our research results indicate that the photocurrent of the ML α-selenium p–n junction optoelectronic device exhibits anisotropy. The maximum photoresponsivity (178.49 <em>a</em><small>₀</small><small>²</small> per photon) in the armchair (ARM) direction is one-half that (341.72 <em>a</em><small>₀</small><small>²</small> per photon) in the zigzag (ZZ) direction. When stress is applied, the most significant modulation of photoresponsivity occurs in the ZZ direction, reaching a value of 613.21 <em>a</em><small>₀</small><small>²</small> per photon. When a gate voltage is applied, the most significant modulation of photoresponsivity occurs in the ARM direction, reaching a value of −684.88 <em>a</em><small>₀</small><small>²</small> per photon. When a thermal difference is applied, the most significant modulation of photoresponsivity occurs in the ARM direction, reaching a value of 412.14 <em>a</em><small>₀</small><small>²</small> per photon. Thus, ML α-selenium in the ZZ direction can be used for photodetection and photosensing, while ML α-selenium in the ARM direction can be used for photosensing. Both strain engineering and temperature differences cause a blueshift in the photocurrent as a function of energy. Our work paves the way for research into low-dimensional monoelemental-material optoelectronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666589","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":"On the relation of structure and dynamics in aromatic ring-tail structured liquids","authors":"Rolf Zeißler, Jan Philipp Gabriel, Dorthe Posselt, Thomas Blochowicz","doi":"10.1039/d4cp04843a","DOIUrl":"https://doi.org/10.1039/d4cp04843a","url":null,"abstract":"We present a combined X-ray and depolarized dynamic light scattering study on a series of liquid phenylalkanes, consisting of an aromatic phenyl ring attached to an alkyl chain of varying length. We study the influence of competing interactions of rings and chains on liquid structure and molecular reorientation. The X-ray scattering curves of the investigated liquids show a weak prepeak in a <em>q</em> range below the main scattering peak, indicating a certain degree of structure formation on a larger length scale than commonly found in simple liquids. As a function of temperature and alkyl chain length, we find that the observed prepeak shares some characteristics with that found for ionic liquids, suggesting a similar origin, <em>i.e.</em>, domains of ring groups separated by alkyl chains leading to nanometer-scale structuring. Furthermore, with increasing chain length, the scattering curves show a distinct transition in the temperature dependence of the prepeak amplitude, which is mirrored in the activation energy of molecular reorientation, obtained <em>via</em> depolarized dynamic light scattering. As a possible interpretation, we suggest that ring–ring interactions control structure as well as dynamics for short alkyl chains but rapidly lose influence above a certain alkyl chain length. Since phenylalkanes are among the most simple representatives of liquids consisting of aromatic and non-aromatic units, we regard this work as a proof of concept to study the coupling of structure and dynamics in liquids with competing interactions weaker than both Coulombic interactions and hydrogen bonding.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"70 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666591","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":"Non-Metal Doped VTe2 Monolayer: Theoretical Insights into the Enhanced Mechanism for Hydrogen Evolution Reaction","authors":"Yanwei Wang, Guofeng Li, Jisong Hu, Ge Gao, Ying Zhang, Guangxia Shi, Xu Yang, Lei Zhang, Ling Fang, Yinwei Li","doi":"10.1039/d5cp00670h","DOIUrl":"https://doi.org/10.1039/d5cp00670h","url":null,"abstract":"Two-dimensional transition metal dichalcogenides (TMDCs), such as vanadium ditelluride (VTe2), have emerged as promising catalysts for the hydrogen evolution reaction (HER) due to their unique layered structures and remarkable electronic properties. However, the catalytic performance of pristine VTe2 remains inferior to that of noble metals. In this study, density functional theory (DFT) calculations were employed to systematically investigate the influence of fourteen different non-metal dopants on the HER activity of VTe2. Our results disclose that N-VTe2, P-VTe2 and As-VTe2 possess exceptional catalytic properties for the HER with the Gibbs free energy of hydrogen adsorption (GH*) values of 0.031, −0.032 and 0.024 eV, respectively. Furthermore, analyses of the geometric and electronic structures reveal that non-metal doping induces localized geometric distortions and charge redistribution, thereby altering the electronic environment of active sites and enhancing catalytic performance. More importantly, a composite descriptor , integrating the bond length between doped non-metal atoms and neighboring V atoms (LNM-M) and the pz band center (pz) of the doped atoms, demonstrates a strong correlation with GH* and may serve as an effective predictor of HER activity. These findings shed light on non-metal doping as an effective strategy for developing efficient, non-noble metal HER catalysts based on TMDCs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"198 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666444","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":"Effect of Halogen Substitution in Spacer Cations on Two-Dimensional Ruddlesden-Popper Perovskites","authors":"Qiang Huang, Xiaoyan Gan, Linfei Yang, Jianhua Liao, Liling Guo, Hanxing Liu","doi":"10.1039/d5cp00707k","DOIUrl":"https://doi.org/10.1039/d5cp00707k","url":null,"abstract":"This research investigated how halogen substitution in spacer cations influenced the crystal and electronic structures of two-dimensional Ruddlesden-Popper perovskites (X-(CH2)2-NH3)2PbI4 (where X can be I, Br, or Cl) through first-principles calculations. In contrast to (I-(CH2)2-NH3)2PbI4, (Br-(CH2)2-NH3)2PbI4 and (Cl-(CH2)2-NH3)2PbI4 exhibited a greater degree of deviation from ideal octahedral geometry. Moreover, the Pb-I-Pb bond angles in (Br-(CH2)2-NH3)2PbI4 and (Cl-(CH2)2-NH3)2PbI4 were approximately 180°, indicating that the distortions of the adjacent [PbI6]4- octahedra were relatively minor. In comparison, (I-(CH2)2-NH3)2PbI4 demonstrated more significant adjacent [PbI6]4- octahedral distortions and therefore larger band gap. The significant distortion of adjacent [PbI6]4- octahedra in (I-(CH2)2-NH3)2PbI4 was found to predominantly induced by hydrogen-bonding interactions between the organic and inorganic components, along with the I-I interactions. In (Br-(CH2)2-NH3)2PbI4 and (Cl-(CH2)2-NH3)2PbI4, the hydrogen-bonding interactions between the spacer cations facilitated the insertion of two carbon atoms into the pocket of the inorganic layer, leading to significant distortion of the individual [PbI6]4- octahedra. Additionally, these hydrogen-bonding interactions significantly contributed to their increased thermal stability. Moreover, the symmetrical positioning of the spacer cations in relation to the inorganic layer led to symmetrical hydrogen-bonding interactions between the organic and inorganic components, which helped prevent the deformation of adjacent [PbI6]4- octahedra. This research provided valuable theoretical insights for the selection of organic cations of two-dimensional organic-inorganic hybrid materials.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"452 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666596","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":"X-ray absorption spectroscopy reveals charge transfer in π-stacked aromatic amino acids","authors":"Carlos Andres Ortiz-Mahecha, Schwob Lucas, Juliette Leroux, Sadia Bari, Robert H Meißner, Annika Bande","doi":"10.1039/d4cp04615c","DOIUrl":"https://doi.org/10.1039/d4cp04615c","url":null,"abstract":"X-ray absorption spectroscopy (XAS) and quantum mechanical calculations bear great potential to unravel π stacking side-chain interaction properties and structure in, e.g., proteins. However, core-excited state calculations for proteins and their associated interpretation for π-π interactions are challenging due to the complexity of the non-covalent interactions involved. A theoretical analysis is developed to decompose the core-to-valence transitions into their atomic contributions in order to characterize the π stacking of aromatic amino acids as a function of their non-covalent distance change. Three models were studied as a non-covalent mixed dimers of the phenylalanine, tyrosine and tryptophan amino acids. We found that there are carbon 1s → π<small>^∗</small> charge transfer transitions associated with the non-covalently paired aromatic amino acids through their side chains. The atomic-centered contributions to the electronic transition density quantify the excited state charge transfer of the pairing amino acid models, highlighting the π stacking interactions between their aromatic side chains.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"20 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666592","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 theoretical investigation of heavy atom and oxidation effects in MR-TADF emitters for OLEDs: a combined DFT, double hybrid DFT, CCSD, and QM/MM approaches","authors":"Singaravel Nathiya, Murugesan Panneerselvam, Luciano T. Costa","doi":"10.1039/d5cp00033e","DOIUrl":"https://doi.org/10.1039/d5cp00033e","url":null,"abstract":"The emerging multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with organoboron and nitrogen cores highlight their significance in OLEDs. However, their efficiency is challenged by slower rate constants in the reverse intersystem crossing (<em>k</em><small>_RISC</small>) process compared to conventional TADF emitters. The study entails an in-depth analysis focused on gaining a better understanding of the photophysical properties of MR-TADF emitters. Using DFT and TD-DFT analyses, 48 MR-TADF molecules are studied, incorporating heavy atoms such as sulfur and selenium, and their subsequent oxidation, and peripheral donors such as carbazole (Cz), <em>tert</em>-butyl-carbazole (<em>t</em>Cz), diphenylacridine (DPAC), and dimethylacridine (DMAC) into organo boron and nitrogen-embedded systems. Moreover, the QM/MM approach was utilized to examine the excited state properties in the crystal phase. A comprehensive assessment of this molecular framework reveals that integrating heavy atoms and donors into MR-TADF molecules results in significant enhancements in Δ<em>E</em><small>_ST</small>, larger SOC, and higher-order radiative (10<small>⁸</small> s<small>⁻¹</small>) rates, leading to faster <em>k</em><small>_ISC</small> (∼10<small>⁸</small> s<small>⁻¹</small>) and <em>k</em><small>_RISC</small> (∼10<small>⁶</small> s<small>⁻¹</small>) rates. Based on key criteria, eight potential molecules were selected and their excited-state properties were precisely analyzed using double-hybrid density functionals including B2PLYP and PBE0-2, along with highly correlated wave function STEOM-DLPNO-CCSD.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"69 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666447","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}