Physical Chemistry Chemical Physics最新文献

{"title":"Comparative study of electron transport through aromatic molecules on gold nanoparticles: insights from soft X-ray spectroscopy of condensed nanoparticle films versus flat monolayer films†","authors":"Shogo Tendo, Akinobu Niozu, Kakuto Yoshioka, Masataka Tabuse, Jun-ichi Adachi, Hirokazu Tanaka and Shin-ichi Wada","doi":"10.1039/D4CP03556A","DOIUrl":"10.1039/D4CP03556A","url":null,"abstract":"<p >Understanding electron transport in self-assembled monolayers on metal nanoparticles (NPs) is crucial for developing NP-based nanodevices. This study investigates ultrafast electron transport through aromatic molecules on NP surfaces <em>via</em> resonant Auger electron spectroscopy (RAES) with a core-hole-clock (CHC) approach. Aromatic molecule-coated Au NPs are deposited to form condensed NP films, and flat monolayers are prepared for comparison. Soft X-ray techniques, including X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy, confirm oriented monolayers in both NP and flat films. The nuclear dynamics is studied <em>via</em> ion yield measurements. After subtracting secondary processes, the ion yield spectra of the condensed NP films reveal site-selective desorption of the methyl ester group by resonant core excitation. The ultrafast electron transport time from the carbonyl group through the phenyl rings to the metal surfaces in the condensed NP films is successfully determined <em>via</em> the RAES-CHC approach by subtracting inelastic scattering components. The chain length of the aromatic molecules influence the electron transport time in the NP films, reflecting the trends observed in the flat films. This evidence supports ultrafast electron transport <em>via</em> the through-bond model, independent of interactions between the molecules adsorbed on an NP itself or adjacent NPs. Identifying and subtracting background spectral components of the condensed NP films allows accurate analysis of the ultrafast dynamics. This study suggests that insights gained from electron transport processes in the flat monolayer films can be extrapolated to practical NP–molecule interfaces, providing valuable insights for the molecular design of NP-based devices.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 388-396"},"PeriodicalIF":2.9,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp03556a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782930","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":"Expression of concern: Localized electropolymerization on oxidized boron-doped diamond electrodes modified with pyrrolyl units","authors":"Paolo Actis, Mael Manesse, Carolina Nunes-Kirchner, Gunther Wittstock, Yannick Coffinier, Rabah Boukherroub and Sabine Szunerits","doi":"10.1039/D4CP90195A","DOIUrl":"10.1039/D4CP90195A","url":null,"abstract":"<p >Expression of concern for ‘Localized electropolymerization on oxidized boron-doped diamond electrodes modified with pyrrolyl units’ by Paolo Actis <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2006, <strong>8</strong>, 4924–4931, https://doi.org/10.1039/B611735J.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 606-606"},"PeriodicalIF":2.9,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp90195a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782931","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":"Defect dependent electronic properties of two- dimensional transition metal dichalcogenides (2H, 1T, 1T’ phase)","authors":"Berna Akgenc Hanedar, Mehmet Cengiz Onbasli","doi":"10.1039/d4cp04017a","DOIUrl":"https://doi.org/10.1039/d4cp04017a","url":null,"abstract":"Transition metal dichalcogenides (TMDs) exhibit a wide range of electronic properties due to their structural diversity. Understanding their defect-dependent properties might enable the design of efficient, bright, and long-lifetime quantum emitters. Here, we use density functional theory (DFT) calculations to investigate the 2H, 1T, and 1T’ phases of MoS2, WS2, MoSe2, WSe2 and the effect of defect densities on the electronic band structures, focusing on the influence of chalcogen vacancies. The 2H phase, thermodynamically stable, is a direct band gap semiconductor, while the 1T phase, despite its higher formation energy, exhibits metallic behavior. 1T’ phases with spin-orbit coupling show significant band inversion 0.61, 0.77, 0.24 and 0.78 eV for MoS2, MoSe2, WS2 and WSe2, respectively. We discovered that for all four MX2 systems, the energy difference between 2H, 1T and 1T’ phases decrease with increasing concentration of vacancy (from %3.13 to %21.88). Our findings show that the 2H phase also has minimum energy values depending on vacancies. TMDs containing W were found to have a wider bandgap compared to those containing Mo. The band gap of 2H WS2 decreased from 1.81 eV (1.54 eV with SOC included) under GGA calculations to a range of 1.37 eV to 0.79 eV, while the band gap of 2H MoSe2 reduced from 1.43 eV (1.31 eV with SOC) under GGA to a range of 0.98 eV to 0.06 eV, depending on the concentration. Our findings offer guidelines for experimental screening of 2D TMD defects, paving the way for the development of next-generation spintronic, electronic, and optoelectronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782933","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":"Pressure-induced polymerization of 1,4-difluorobenzene towards fluorinated diamond nanothreads","authors":"Guangwei Che, Yunfan Fei, Xingyu Tang, Zilin Zhao, Takanori Hattori, Jun Abe, Xiaoge Wang, Jing Ju, Dong Xiao, Yajie Wang, Kuo Li, Haiyan Zheng","doi":"10.1039/d4cp03751k","DOIUrl":"https://doi.org/10.1039/d4cp03751k","url":null,"abstract":"Pressure-induced polymerization (PIP) of aromatic molecules has emerged to be an effective method for synthesizing various carbon-based materials. The selection of suitable functionalized molecular precursors is crucial for obtaining the desired structures and functions. In this work, 1,4-difluorobenzene (1,4-DFB) was selected as the building block for PIP. In situ high-pressure investigations of 1,4-DFB reveals a phase transition at approximately 12.0 GPa and an irreversible chemical reaction at 18.7 GPa. Structural analysis of the product and the kinetics of the reaction uncovered the formation of pseudo-hexagonal stacked fluoro-diamond nanothreads with linear growth. Compared to the crystal structures of benzene under high pressure, 1,4-DFB exhibits higher compression along the [001] axis. The anisotropic compression is attributed to the stronger H…π interaction along the [011 @#x0305;] axis and the potential compression-inhibiting H…F interactions along the [100] and [010] axes, and it facilitates a possible reaction pathway along the [011 @#x0305; ] axis. This work emphasizes the crucial role of functionalization in modulating molecular stacking and influencing the reaction pathway.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"81 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782935","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":"Recent Process in Doping Engineering of Perovskite Oxides for Photocatalytic Green Hydrogen Production via Water Splitting","authors":"Jieding Wei, Shuo Wang, Yucheng Huang, Manman Shi","doi":"10.1039/d4cp03622k","DOIUrl":"https://doi.org/10.1039/d4cp03622k","url":null,"abstract":"Given the immense potential for addressing energy and environmental issues, the utilization of solar energy for hydrogen production by water splitting has garnered widespread attention in the scientific community. Perovskite oxides (POs), with their compositional flexibility and structural stability, hold significant promise in photocatalytic hydrogen evolution reaction (HER). Rational doping of POs is the key to enhancing the rate of photocatalytic HER. In this review, with the aim of providing guidance for the enhancement in photocatalytic efficiency, the recent advancements in ion-doping engineering of PO-based photocatalysts are summarized. The principles of photocatalytic water splitting, the preparation methods of ion-doped POs, the types of dopants, and the effects of doping on the photocatalytic performance of HER are systematically reviewed and discussed. Ultimately, the prospects and challenges of the doped POs for the photocatalytic HER are proposed. This review provides a good reference for making informed decisions regarding the selection of doped ions and a valuable suggestion for establishing high-stability photocatalytic systems toward large-scale applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783153","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":"αnhm-GeSe: a multifunctional semiconductor combining auxeticity and piezoelectricity†","authors":"Jiajun Zhu, Heyun Zhao and Wanbiao Hu","doi":"10.1039/D4CP04045G","DOIUrl":"10.1039/D4CP04045G","url":null,"abstract":"<p >Multifunctional materials with outstanding performance have enormous potential applications in the next generation of nanodevices. Using first principles calculations, we design a series of multifunctional two-dimensional materials in monolayer α<small>_<em>n</em></small>h<small>_<em>m</em></small>-GeSe (<em>n</em>, <em>m</em> = 1, 2) that combine auxeticity and piezoelectricity. Due to the similar local structures of α-GeSe and h-GeSe, monolayer α<small>_<em>n</em></small>h<small>_<em>m</em></small>-GeSe can be designed through the combination of these two materials. Elastic constants and phonon dispersion curves confirm that all the structures are mechanically and dynamically stable. Monolayer α<small>_<em>n</em></small>h<small>_<em>m</em></small>-GeSe exhibits auxetic properties with an in-plane negative Poisson's ratio along the diagonal direction. An out-of-plane negative Poisson's ratio effect can be observed by applying tensile strain in the <em>x</em>-direction, which is beneficial for mechanical devices. Only a few materials are both in-plane and out-of-plane auxetic. In addition, monolayer α<small>_<em>n</em></small>h<small>_<em>m</em></small>-GeSe can exhibit electric polarization because of the breaking of the central symmetry, demonstrating in-plane piezoelectric properties with strong anisotropy. The above results make monolayer α<small>_<em>n</em></small>h<small>_<em>m</em></small>-GeSe an interesting multifunctional material and provide a candidate material for a nanoscale device.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 325-330"},"PeriodicalIF":2.9,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782934","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":"Acoustic shock wave-induced superheating-assisted dynamic recrystallization – a case study of d-tartaric acid†","authors":"Sivakumar Aswathappa, Lidong Dai, Sahaya Jude Dhas Sathiyadhas and Raju Suresh Kumar","doi":"10.1039/D4CP03750B","DOIUrl":"10.1039/D4CP03750B","url":null,"abstract":"<p >Superheating-assisted melting and crystallization are prominent subjects in condensed matter physics. However, understanding the superheating concepts under acoustic shocked conditions remains a mystery. Herein, we demonstrate superheating on the basis of dynamic recrystallization in a <small>D</small>-tartaric acid powder sample, which nearly attains an ideal crystal structure and morphology under the 100-shocked conditions compared to the control sample and the obtained results are evaluated by conventional diffraction, spectroscopic and microscopic techniques. From the XRD results, the intensities of the planes (100) and (110) are found to have increased under the 100-shocked conditions, whereas the intensity ratio (011)/(110) has been significantly reduced. Moreover, the intensity ratio of major internal Raman modes such as <em>v</em><small>_C–O</small> (1694 and 1700 cm<small>⁻¹</small>), <em>v</em><small>_C–H</small> (2933 and 2967 cm<small>⁻¹</small>) and <em>v</em><small>_O–H</small> (3331 and 3403 cm<small>⁻¹</small>) has been considerably modified with respect to the number of shock pulses such that the sample produces an ideal Raman spectrum of <small>D</small>-tartaric acid, and thereby the intensities of the lattice Raman modes also support this claim. Most importantly, the SEM results demonstrate the formation of an ideal morphology of <small>D</small>-tartaric acid from the irregular morphological pattern upon exposure to 100 shocks due to the superheating and dynamic recrystallization process. The proposed technique is strongly suggested for materials processing to enhance technological significance for all classes and scales of materials.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 1","pages":" 308-315"},"PeriodicalIF":2.9,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782985","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 study of hydrogen storage properties of Irida-graphene","authors":"Yanhong Sun, Yuhong Chen, Menglin Yang, Kun Zhou, Jialin Sun, Kongyang Zhao, Lai Xu","doi":"10.1039/d4cp03381g","DOIUrl":"https://doi.org/10.1039/d4cp03381g","url":null,"abstract":"The hydrogen storage properties of the 2D carbon allotrope Irida-graphene (IG) were investigated using first-principles calculation. The intrinsic IG adsorption energy for H2 is only -0.06 eV, significantly lower than the effective adsorption threshold. To improve its hydrogen storage capabilities, IG was doped with boron (B) and modified with sodium (Na). It was found that both 2Na@IG and 2Na@BIG systems could adsorb 8 pairs of H2. However, the average adsorption energy of H2 in the 2Na@BIG system (-0.145 eV) is higher compared to that in the 2Na@IG system (-0.134 eV), and the adsorption capacity (14.6 wt.%) was superior to that of the 2Na@IG system (14.5 wt.%). The introduction of B created an electron-deficient structure (BIG), enhancing electron transfer between Na and the substrate to improve Na binding energy. This enhancement resulted in stronger polarization and orbital hybridization of H2 within the 2Na@BIG system compared to the 2Na@IG system, further boosting its adsorption performance. The charge transfer between Na and the substrate generated an electric field that polarized H2 adsorbed around Na, while the electric field generated by the already polarized H2 further polarizes the H2 adsorbed in the outer layer. Density of States(DOS) diagrams illustrated orbital hybridization of the H2 in both systems. Molecular dynamics simulations conducted at room temperature(300K) demonstrated that the 2Na@BIG system achieved a hydrogen storage capacity of 8.8 wt.%. In conclusion, both 2Na@IG and 2Na@BIG systems exhibit potential as H2 storage materials, but the 2Na@BIG system displays superior hydrogen storage performance compared to the 2Na@IG system.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783201","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":"Structural Complexity of Glyphosate and Aminomethylphosphonate Metal Complexes","authors":"Olivia Rusli, Oscar Hamilton Lloyd Williams, Papri Chakraborty, Marco Neumaier, Frank Hennrich, Sjors Bakels, Kevin Hes, Anouk Rijs, Boris Ucur, Shane Ellis, River Jack Pachulicz, Tara Louise Pukala, Nicole Joy Rijs","doi":"10.1039/d4cp04019h","DOIUrl":"https://doi.org/10.1039/d4cp04019h","url":null,"abstract":"Small differences in the structure and subsequent reactivity of glyphosate complexes can have a highly consequential impact due to the enormous quantities of glyphosate used globally. The gas phase metal speciation of glyphosate and its abundant metabolite, aminomethylphosphonic acid (AMPA), were determined using cross-platform electrospray ionisation ion mobility mass spectrometry. Monomeric [M+L−H]<small>⁺</small> complexes, and both larger, and/or higher order clusters formed with divalent metals (M = Mg<small>²⁺</small>, Ca<small>²⁺</small>, Sr<small>²⁺</small>, Ba<small>²⁺</small>, Mn<small>²⁺</small>, Co<small>²⁺</small>, Cu<small>²⁺</small>, and Zn<small>²⁺</small>; and L = glyphosate and AMPA). Complexation occurred at more than one ligand donor site for [M+L−H]<small>⁺</small>, resulting in multidentate complexes. The type of complex depended on M, with central positions maximizing the interactions of the M with donor sites of the L preferred. The isomers were separated by ion mobility and experimental collisional cross sections (<small>^N2</small>CCS<small>_exp</small>) were derived for all isolated species. An energy threshold DFT approach located the structural families and potential lowest energy forms; these were found to be consistent with confirmed condensed phase (reported crystal structures) and gas phase structures (via infrared multiphoton dissociation, IRMPD). Theoretical nitrogen collisional cross sections (<small>^N2</small>CCS<small>_calc</small>) of these confirmed structures tended to underestimate the <small>^N2</small>CCS<small>_exp</small> for both [M+glyphosate−H]<small>⁺</small> and [M+AMPA−H]<small>⁺</small> complexes. Underestimation ranged between 1 - 20%, and was not uniform between species. By comparison, helium collisional cross sections (<small>^He</small>CCS<small>_exp</small> and <small>^He</small>CCS<small>_calc</small>) were in better agreement (within 1-3%). These findings suggest further refinements are needed to collisional cross section modelling for metal containing species, in particular for nitrogen drift gas.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"13 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782986","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":"Urea Hydrogen-Bond Donor Strengths: Bigger is not Always Better","authors":"Celine Nieuwland, Angelina van Dam, F. Matthias Bickelhaupt, Célia Fonseca Guerra","doi":"10.1039/d4cp04042b","DOIUrl":"https://doi.org/10.1039/d4cp04042b","url":null,"abstract":"The hydrogen-bond donor strength of ureas, widely used in hydrogen-bond donor catalysis, molecular recognition, and self-assembly, can be enhanced by increasing the size of the chalcogen X in the C=X bond from O to S to Se and by introducing more electron-withdrawing substituents because both modifications increase the positive charge on the NH groups which become better hydrogen-bond donors. However, in 1,3-diaryl X-ureas, a steric mechanism disrupts the positive additivity of these two tuning factors, as revealed by our quantum-chemical analyses. This leads to an enhanced hydrogen-bond donor strength, despite a lower NH acidity, for 1,3-diaryl substituted O-ureas compared to the S- and Se-urea analogs. In addition, we provide a strategy to overcome this steric limitation using a predistorted urea-type hydrogen-bond donor featuring Group 14 elements in the C=X bond so that the hydrogen-bond donor strength of X-urea derivatives bearing two aryl substituents can be enhanced upon varying X down Group 14.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777126","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}