Physical Chemistry Chemical Physics最新文献_第3页

Machine learning with new functional structure descriptors for design and screening of ionic liquids in CO2 efficient capture 机器学习与新的功能结构描述符设计和筛选离子液体在二氧化碳有效捕获

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-17 DOI: 10.1039/d5cp01972a

Ranran Geng, Wenjuan Deng, Zhiqiang Hu, JianLei Wang, Yuanyuan Zhao, Baichaun Zhou, Guocai Tian

{"title":"Machine learning with new functional structure descriptors for design and screening of ionic liquids in CO2 efficient capture","authors":"Ranran Geng, Wenjuan Deng, Zhiqiang Hu, JianLei Wang, Yuanyuan Zhao, Baichaun Zhou, Guocai Tian","doi":"10.1039/d5cp01972a","DOIUrl":"https://doi.org/10.1039/d5cp01972a","url":null,"abstract":"Carbon dioxide emission reduction, conversion and utilization are the hot and difficult issues in the world. As a new kind of green solvents, ionic liquids (ILs) are widely used in CO2 capture and conversion, but there are various kinds of ILs (more than 1018). How to select and screen the appropriate ILs for CO2 capture is an urgent problem to be solved. Therefore, it is of great significance to establish the Quantitative Structure-Property Relationships (QSPR) of ILs for CO2 capture. From the practical point of view of ILs design and synthesis, a new functional structure descriptor (FSD) based on group contribution method (GC) was constructed. At the same time, the idea of increasing dimension to increase accuracy in traditional machine learning is changed, and the feasibility of reducing the dimension under the condition of ensuring accuracy is examined. A dimensionless molecular descriptor CORE is constructed. Based on these two new molecular descriptors, we discussed the performance of six common ensemble learning models (CatBoost, LightGBM, XGBoost, GBDT, RF and AdaBoost) for CO2 solubility in ILs. It is shown that all ensemble learning models can achieve good performance, but CatBoost model is the most outstanding. The R² of 0.9945 and MAE of 0.0108 for CatBoost-FSD model is achieved, while R² and MAE is 0.9925 and 0.0120 for CatBoost-CORE model, respectively. The interpretability of CatBoost-CORE model is analyzed, and the key features are determined. Based on the CORE descriptor, the best experimental conditions are obtained, and nine kinds of ILs with superior performance are recommended.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305474","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}

引用次数: 0

Optical properties of sarcosine crystal under hydrostatic pressure: a DFT-based computational study 静水压力下肌氨酸晶体光学性质的dft计算研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-17 DOI: 10.1039/d5cp01046b

Geanso M. de Moura, Sérgio Alves de Azevedo, Julio Ricardo Sambrano, Mateus R. Lage, Adenilson O. dos Santos, Stanislav R. Stoyanov, T. Andrade-Filho

{"title":"Optical properties of sarcosine crystal under hydrostatic pressure: a DFT-based computational study","authors":"Geanso M. de Moura, Sérgio Alves de Azevedo, Julio Ricardo Sambrano, Mateus R. Lage, Adenilson O. dos Santos, Stanislav R. Stoyanov, T. Andrade-Filho","doi":"10.1039/d5cp01046b","DOIUrl":"https://doi.org/10.1039/d5cp01046b","url":null,"abstract":"Organic crystals have become attractive for applications as nonlinear optical materials due to their nonlinear susceptibility, optical transparency, and other properties that can be tuned using elevated pressure. We have investigated the optical properties of the zwitterionic crystal of the natural amino acid sarcosine using the first-principles projected augmented plane wave method and the GGA and hybrid exchange-correlation functionals. The molecular crystal of sarcosine is composed of zwitterion organic molecules arranged in an antiparallel fashion by the formation of distinct hydrogen bond chains in the planes (100), (010), and (001). The calculated anisotropic optical properties of sarcosine, including the dielectric constant, absorption, extinction coefficient, refractive index, reflectivity, energy loss function, and optical conductivity, are determined from ambient to 3.7 GPa hydrostatic pressure along crystallographic axes a, b, and c. Sarcosine has an optical anisotropy at ambient and external hydrostatic pressures, characterized by specific peaks in the ultraviolet spectrum. The results show the potential application of the studied system in nonlinear optics, UV detectors, and high-pressure photonic applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329123","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}

引用次数: 0

Complex active site structures influence absorption spectrum of Chrimson wild type and mutants 复杂的活性位点结构影响野生型和突变体的吸收光谱

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-17 DOI: 10.1039/d5cp00762c

Katharina Spies, Beatrix M. Bold, Marcus Elstner

引用次数: 0

Pre-trained Language Models for Protein and Molecular Design 蛋白质和分子设计的预训练语言模型

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp00785b

Erdong Zhang, Calvin Yu-Chian Chen, Zilin Pan, Zequan Yao, Tiejun Dong, Guan-Xing Chen, Tingwen Deng, Shiwei Chen

引用次数: 0

The orientation design of high-polarity ligand dipole CF3-PEA for enhancing the surface stability and optoelectronic properties of the FAPbI3 perovskite. 高极性配体偶极子CF3-PEA的取向设计提高了FAPbI3钙钛矿的表面稳定性和光电性能。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp00612k

Xiuchen Han,Qi Yang,Shuning Wang,Xinyue Zhang,Dongmeng Chen,Peiwen Xiao,Wenjing Fang,Bing Liu

{"title":"The orientation design of high-polarity ligand dipole CF3-PEA for enhancing the surface stability and optoelectronic properties of the FAPbI3 perovskite.","authors":"Xiuchen Han,Qi Yang,Shuning Wang,Xinyue Zhang,Dongmeng Chen,Peiwen Xiao,Wenjing Fang,Bing Liu","doi":"10.1039/d5cp00612k","DOIUrl":"https://doi.org/10.1039/d5cp00612k","url":null,"abstract":"Ligand dipoles are introduced onto perovskite surfaces to enhance the optoelectronic properties and stability of organic-inorganic hybrid perovskite solar cells (PSCs), achieving diverse spatial distributions and orientational variations due to their interaction. However, the impacts of ligand dipole orientation on the performance of PSCs remain unclear. In this work, we investigate the adsorption of high-polarity ligand dipole 4-trifluoromethyl-phenethylammonium (CF3-PEA) with orientation design on the PbI2-terminated surface of the formamidinium perovskite (FAPbI3), revealing the impact of CF3-PEA orientation on the atomic structure, stability, and optoelectronic properties of the FAPbI3 surface. The results indicate that on the FAPbI3 surface along with the (001) crystal plane, the optimal crystal orientation of CF3-PEA is [2, 4, -1], where the strong -NH3/π⋯I interaction results in the parallel alignment of CF3-PEA with the FAPbI3 surface. Under the optimal [2, 4, -1] orientation, the surface adsorption system exhibits the lowest relative total energy difference (0 eV), formation energy (-0.746 eV) and adsorption energy (-4.14 eV) among all adsorption systems, with the formation energy being 1.54 times those of bare FAPbI3, revealing its highest stability. Moreover, the adsorption of CF3-PEA with [2, 4, -1] orientation results in a decrease of the work function from 6.764 eV of bare FAPbI3 to 6.743 eV due to the strong -NH3/π⋯I interaction with significant charge transfer. Furthermore, the appearance of sub-bandgap states in density of states leads to an obvious redshift in the light absorption coefficient attributed to structural distortions, which indicates that the optoelectronic properties of FAPbI3 are improved. This work provides insights into optimizing the performance of PSCs by regulating the orientation of ligand dipoles.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"103 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144295828","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}

引用次数: 0

On the structure of hybrid water-in-salt electrolytes. 盐包水杂化电解质的结构研究。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp00680e

Raúl Lois-Cuns,Antía Santiago-Alonso,Martín Otero-Lema,Juan J Parajó,Josefa Salgado,Hadrián Montes-Campos,Trinidad Méndez-Morales,Luis M Varela

引用次数: 0

Intermolecular organization in aqueous mixtures of choline lysinate studied by NMR and molecular dynamics/quantum mechanics 用核磁共振和分子动力学/量子力学研究了溶解胆碱水溶液中的分子间组织

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp00861a

Einaras Sipavičius, Lukas Mikalauskas, Vytautas Klimavičius, Kęstutis Aidas

{"title":"Intermolecular organization in aqueous mixtures of choline lysinate studied by NMR and molecular dynamics/quantum mechanics","authors":"Einaras Sipavičius, Lukas Mikalauskas, Vytautas Klimavičius, Kęstutis Aidas","doi":"10.1039/d5cp00861a","DOIUrl":"https://doi.org/10.1039/d5cp00861a","url":null,"abstract":"Aiming to scrutinize intermolecular organization in aqueous mixtures of choline lysinate, [Cho][Lys], ionic liquid (IL), the dependences of the 1H NMR chemical shifts and diﬀusion coeﬃcients on their composition were measured. To rationalize experimental ﬁndings, extensive molecular dynamics (MD) simulations and linear response quantum mechanics/molecular mechanics (QM/MM) computations of NMR shielding constants were performed. Analysis of MD trajectories reveals that extent of intermolecular contacts between cations and anions intensiﬁes with the increasing content of the IL in the mixture. Moreover, the tendency of choline cations and the side chains of lysinate anions to self-aggregate was observed as well, leading to the formation of a continuous, highly polar domain composed of choline cations and the carboxylate groups of lysinate anions, as well as a less polar domain formed by the side chains of the anions in IL-rich mixtures. Under these circumstances, isolated water pockets are found to be situated at the interface of the polar and nonpolar ionic domains. The dependences of the measured diﬀusion coeﬃcients on the composition of the mixture reveals the existence of two dynamical regimes – fast and slow regimes below and above molar fraction of the IL of 11%, respectively. Results of MD simulations suggest that – at this speciﬁc molar composition of aqueous [Cho][Lys] mixture – continuous water network ceases giving way to the continuous structure of ionic domains being formed. The QM/MM results for the 1H NMR chemical shifts of aqueous IL mixtures generally agree well with experimental ﬁndings and corroborate structural results. The prominent upﬁeld shift of the NMR signal of protons in fast exchange with the rising content of the IL was successfully rationalized.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"34 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305478","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}

引用次数: 0

Construction of First Principle Based Adiabatic and Diabatic Hamiltonian for TiO68- unit of BaTiO3 Crystal: Photoemission Spectra and Ferroelectricity 基于第一性原理的BaTiO3晶体TiO68-单元的绝热和非绝热哈密顿量的构建：光发射光谱和铁电性

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp01761k

Mantu Kumar Sah, Soumya Mukherjee, Satrajit Adhikari, Satyam Ravi

{"title":"Construction of First Principle Based Adiabatic and Diabatic Hamiltonian for TiO68- unit of BaTiO3 Crystal: Photoemission Spectra and Ferroelectricity","authors":"Mantu Kumar Sah, Soumya Mukherjee, Satrajit Adhikari, Satyam Ravi","doi":"10.1039/d5cp01761k","DOIUrl":"https://doi.org/10.1039/d5cp01761k","url":null,"abstract":"The ferroelectric property of BaTiO3 crystal arises from the strong Pseudo Jahn-Teller (PJT) interactions between the non-degenerate ground electronic state, 1A1g and the degenerate 1T1u symmetry states through the nuclear distortions of t1u modes in TiO68- unit. In a d0 electronic conﬁguration of Ti4+ ion, the PJT interaction leads to a stabilization eﬀect, which has been explored using Beyond Born-Oppenheimer (BBO) theory. The 1T1u excited states form a three-state degeneracy, exhibiting feeble Jahn-Teller (JT) distortions over the t2g planes. For the ﬁrst time, we compute ab initio adiabatic potential energy surfaces (PESs) and non-adiabatic coupling terms (NACTs), and thereafter, diabatic PESs and couplings for the perovskite unit, TiO68-. Using a Time-Dependent Discrete Variable Representation (TDDVR) approach, the theoretical photoemission spectra exhibit good agreement with the experimental ones. Moreover, the experimental observation on order parameter associated with ferroelectric properties of BaTiO3 crystal show close resemblance with present and other theoretical predictions.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296230","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}

引用次数: 0

Recent advances in CeO2 based abrasives for chemical mechanical polishing. 化学机械抛光用CeO2基磨料的研究进展。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp00778j

Yongxin Wang,Yunhui Shi,Jiabao Cheng,Yao Xu,Yizhan Wang,Jiawei Qiu

引用次数: 0

Photodimerization of norbornenes and cyclohexenes catalyzed by Cu(I) complexes: mechanistic similarities and differences. Cu(I)配合物催化降冰片烯和环己烯的光二聚化：机理的异同。

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-16 DOI: 10.1039/d5cp01567g

Xin-Xin Liu,Jia-Jia Ma,Guo Li,Ling-Ya Peng,Qiu Fang,Wei-Hai Fang,Ganglong Cui

{"title":"Photodimerization of norbornenes and cyclohexenes catalyzed by Cu(I) complexes: mechanistic similarities and differences.","authors":"Xin-Xin Liu,Jia-Jia Ma,Guo Li,Ling-Ya Peng,Qiu Fang,Wei-Hai Fang,Ganglong Cui","doi":"10.1039/d5cp01567g","DOIUrl":"https://doi.org/10.1039/d5cp01567g","url":null,"abstract":"The Cu(I)-photocatalyzed cycloaddition reaction has become an important way to construct four-membered ring products. A recent experiment reported the photocycloaddition of norbornenes (nb) and cyclohexenes (ch) catalyzed by CuOTf. However, the atomic level details remain lacking. Herein, using high-level electronic structure methods, the initial photophysics and subsequent dimerization reaction of two Cu complexes ([Cu(nb)2]+ and [Cu(ch)2]+) were explored. For both species, the 1MLCT state is initially populated and there are two triplet states (3MLCT and 3LC). Notably, in [Cu(ch)2]+, an additional 1LC state appears near 1MLCT rendering 1MLCT short-lived and difficult to detect experimentally as a result of an ultrafast internal conversion to 1LC. Through direct and 3MLCT-mediated intersystem crossing, the lowest 3LC state is populated. The most striking difference of the 3LC structures of [Cu(ch)2]+ and [Cu(nb)2]+ is that one cyclohexene of the former undergoes a half-chair-to-chair conformational change while the latter does not. From the precursor 3LC, two successive but nonadiabatic reactions form two C-C bonds in the 3LC and S0 states, respectively. The current work provides the first efforts to understand the atomistic details of the Cu-catalyzed dimerization of norbornenes and cyclohexenes and paves a way for rationally designing superior photocatalysts for olefins dimerization.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"228 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144295826","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}

引用次数: 0