【期刊】Welcome to Issue 4 of Chin. J. Chem. Phys. | 化学物理学报
Experimental Consideration of Two-Dimensional Fourier Transform Spectroscopy
二维傅里叶变换光谱实验方法简介
周梁，田烈，张文凯*
Two-dimensional Fourier transform (2D FT) spectroscopy is an important technology that developed in recent decades and has many advantages over other ultrafast spectroscopy methods. Although 2D FT spectroscopy provides great opportunities for studying various complex systems, the experimental implementation and theoretical description of 2D FT spectroscopy measurement still face many challenges, which limits their wide application. Recently, the 2D FT spectroscopy reaches maturity due to many new developments which greatly reduces the technical barrier in the experimental implementation of the 2D FT spectrometer. There have been several different approaches developed for the optical design of the 2D FT spectrometer, each with its own advantages and limitations. Thus, a procedure to help an experimentalist to build a 2D FT spectroscopy experimental apparatus is needed. This tutorial review is intending to provide an accessible introduction for a beginner to build a 2D FT spectrometer.
Key words: Two-dimensional Fourier transform spectroscopy, Two-dimensional infrared spectroscopy, Two-dimensional electronic spectroscopy
DOI: 10.1063/1674-0068/cjcp2007125
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Doping Copper Ions in a Metal-Organic Framework (UiO-66-NH2): Location Effect Examined by Ultrafast Spectroscopy
金属有机框架材料UiO-66-NH2中的铜离子掺杂位置效应及相关动力学研究
刘佳，江申龙，张群*
We constructed two types of copper-doped metal-organic framework (MOF), i.e., Cu@UiO- 66-NH2 and Cu-UiO-66-NH2. In the former, Cu2+ ions are impregnated in the pore space of the amine-functionalized, Zr-based UiO-66-NH2; while in the latter, Cu2+ ions are incorporated to form a bimetal-center MOF, with Zr4+ being partially replaced by Cu2+ in the Zr−O oxo-clusters. Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state is promoted for both Cudoped MOFs relative to undoped one, but in a sequence of Cu-UiO-66-NH2>Cu@UiO-66-NH2>UiO-66-NH2. Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs. These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system, further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.
Key words: Metal-organic framework, Copper doping, Location effect, Ultrafast dynamics, Transient absorption spectroscopy, Photocatalysis
DOI: 10.1063/1674-0068/cjcp2005070
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Experimental and Theoretical Study on p-Chlorofluorobenzene in the S0, S1 and D0 States
对氯氟苯S0, S1和D0态的实验与理论研究
凡佳囡，崔婷婷，秦正波*，郑贤锋*，崔执凤
The geometric structures and vibration frequencies of para-chlorofluorobenzene (p-ClFPh) in the first excited state of neutral and ground state of cation were investigated by resonanceenhanced multiphoton ionization and slow electron velocity-map imaging. The infrared spectrum of S0 state and absorption spectrum for S1←S0 transition in p-ClFPh were also recorded. Based on the one-color resonant two-photon ionization spectrum and two-color resonant two-photon ionization spectrum, we obtained the adiabatic excited-state energy of p-ClFPh as 36302±4 cm−1 . In the two-color resonant two-photon ionization slow electron velocity-map imagin spectra, the accurate adiabatic ionization potential of p-ClFPh was extrapolated as 72937±8 cm−1 via threshold ionization measurement. In addition, FranckCondon simulation was performed to help us confidently ascertain the main vibrational modes in the S1 and D0 states. Furthermore, the mixing of vibrational modes between S0→S1 and S1→D0 has been analyzed.
Key words: Resonance-enhanced multiphoton ionization, Slow electron velocity-map imaging, Duschinsky mixing, para-Chlorofluorobenzene
DOI: 10.1063/1674-0068/cjcp2001005
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Population Change of OH and H2O in Water Vapor Glow Discharge Measured Using Concentration Modulation Spectroscopy
用浓度调制光谱法测量水汽辉光放电中OH和H2O的布居数变化
李宝，王莉，方波，赵卫雄，邓伦华*，徐淮良
A distributed feedback laser with a wavelength of 2.8 µm was used to measure the species produced by water vapor glow discharge. Only the absorption spectra of OH radicals and transient H2O molecules were observed using concentration modulation (CM) spectroscopy. The intensities and orientations of the absorption peaks change with the demodulation phase, but the direction of one absorption peak of H2O is always opposite to the other peaks. The different spectral orientations of OH and H2O reflect the increase or the decrease of the number of particles in the energy levels. If more transient species can be detected in the discharge process, the dynamics of excitation, ionization, and decomposition of H2O can be better studied. This study shows that the demodulation phase relationship of CM spectrum can be used to study the population change of molecular energy levels.
Key words: Glow discharge, OH radical, Concentration modulation spectroscopy, Population change
DOI: 10.1063/1674-0068/cjcp2001010
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Geometric and Electronic Structures of Pyrazine Molecule Chemisorbed on Si(100) Surfaceby XPS and NEXAFS Spectroscopy
吡嗪分子在硅(100)面吸附构型的XPS和NEXAFS谱理论研究
宋秀能，季桓宇，林娟，王若宇，马勇*，王传奎
The geometric and electronic structures of several possible adsorption configurations of the pyrazine (C4H4N2) molecule covalently attached to Si(100) surface, which is of vital importance in fabricating functional nano-devices, have been investigated using X-ray spectroscopies. The Carbon K-shell (1s) X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations. Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations. In contrast to the XPS spectra, it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100) systems can be well utilized for structural identification. In addition, according to the classification of carbon atoms, the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.
Key words: Chemisorption/physisorption, Adsorbates on surfaces, X-ray absorption spectroscopy, Photoemission and photoelectron spectra
DOI: 10.1063/1674-0068/cjcp1910180
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Two-Dimensional GaTe/Bi2Se3 Heterostructure: a Promising Direct Z-scheme Water Splitting Photocatalyst
二维GaTe/Bi2Se3异质结：一类有潜力的Z型光解水催化剂
田淑敏，孟杰，黄静*，李群祥*
Among various photocatalytic materials, Z-scheme photocatalysts have drawn tremendous research interest due to high photocatalytic performance in solar water splitting. Here, we perform extensive hybrid density functional theory calculations to explore electronic structures, interfacial charge transfer, electrostatic potential profile, optical absorption properties, and photocatalytic properties of a proposed two-dimensional (2D) small-lattice-mismatched GaTe/Bi2Se3 heterostructure. Theoretical results clearly reveal that the examined heterostructure with a small direct band gap can effectively harvest the broad spectrum of the incoming sunlight. Due to the relative strong interfacial built-in electric field in the heterostructure and the small band gap between the valence band maximum of GaTe monolayer and the conduction band minimum of Bi2Se3 nanosheet with slight band edge bending, these photogenerated carriers transfer via Z-scheme pathway, which results in the photogenerated electrons and holes effectively separating into the GaTe monolayer and the Bi2Se3nanosheet for the hydrogen and oxygen evolution reactions, respectively. Our results imply that the artificial 2D GaTe/Bi2Se3 is a promising Z-scheme photocatalyst for overall solar water splitting.
Key words: Z-scheme photocatalyst, Interfacial built-in electric field, Band edge alignment, Water splitting
DOI: 10.1063/1674-0068/cjcp2006081
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Effect of Passivation on Piezoelectricity of ZnO Nanowire
表面钝化对ZnO纳米线压电性的影响
陈功*，王攀硕
Surface passivation is one valuable approach to tune the properties of nanomaterials. The piezoelectric properties of hexagonal [001] ZnO nanowires with four kinds of surface passivations were investigated using the first-principles calculations. It is found that in the 50% H(O) and 50% Cl(Zn), 50% H(O) and 50% F(Zn) passivations, the volume and surface effects both enhance the piezoelectric coefficient. This differs from the unpassivated cases where the surface effect was the sole source of piezoelectric enhancement. In the 100% H, 100% Cl passivations, the piezoelectric enhancement is not possible since the surface effect is screened by surface charge with weak polarization. The study reveals that the competition between the volume effect and surface effect influences the identification of the diameter-dependence phenomenon of piezoelectric coefficients for ZnO nanowires in experiments. Moreover, the results suggest that one effective means of improving piezoelectricity of ZnO nanowires is shrinking axial lattice or increasing surface polarization through passivation.
Key words: Piezoelectricity, ZnO nanowire, Passivation, First-principles calculation
DOI: 10.1063/1674-0068/cjcp1911208
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Topological Transition in Monolayer Blue Phosphorene with Transition-Metal Adatom under Strain
应力作用下吸附过渡金属原子的蓝磷单层中的拓扑转变
胡格，胡军*
We carried out first-principles calculations to investigate the electronic properties of the monolayer blue phosphorene (BlueP) decorated by the group-IVB transition-metal adatoms (Cr, Mo and W), and found that the Cr-decorated BlueP is a magnetic half metal, while the Mo- and W-decorated BlueP are semiconductors with band gaps smaller than 0.2 eV. Compressive biaxial strains make the band gaps close and reopen, and band inversions occur during this process, which induces topological transitions in the Mo-decorated BlueP (with strain of −5.75%) and W-decorated BlueP (with strain of −4.25%) from normal insulators to topological insulators (TIs). The TI gap is 94 meV for the Mo-decorated BlueP and 218 meV for the W-decorated BlueP. Such large TI gaps demonstrate the possibility to engineer topological phases in the monolayer BlueP with transition-metal adatoms at high temperature.
Key words: Topological transition, Monolayer Blue phosphorene, Biaxial strain, Transition-metal adatom
DOI: 10.1063/1674-0068/cjcp2005061
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Theoretical Studies on Dihedral Angle-Bending Isomers of M2Pt2 0/− Clusters
二面角弯曲异构体：M2Pt2 0/− 团簇的理论研究
曹国进*，贾秀东
The structures and electronic properties of the gaseous M2Pt2 0/− clusters (M represents the alkaline earth metal) were investigated using the density functional theory (B3LYP and PBE0) and wave function theory (SCS-MP2, CCSD and CCSD (T)). The results indicate that the D2h isomers with the planar structures are more stable than the C2v isomers with smaller dihedral angles and shorter Pt-Pt bond lengths. The mutual competition of M(s,p)- Pt(5d) interaction and Pt-Pt covalent bonding contributes to the different stabilizations of the two kinds of isomers. The M(s,p)-Pt(5d) interaction favors the planar isomers with D2h symmetry, while the Pt-Pt covalent bonding leads to the C2v isomers with bending structures. Two different crossing points are determined in the potential energy curves of Be2Pt2 with the singlet and triplet states. But there is just one crossing point in potential energy curves of Ra2Pt2 and Ca2Pt2− because of flatter potential energy curves of Ra2Pt2with the triplet state or Ca2Pt2− with quartet state. The results reveal a unique example of dihedral angle-bending isomers with the smallest number of atoms and may help the understanding of the bonding properties of other potential angle-bending isomers.
Key words: Platinum, Alkaline earth metals, Angle-bending isomer, Dihedral angle
DOI: 10.1063/1674-0068/cjcp2001002
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Theoretical Investigation on QSAR of (2-Methyl-3-biphenylyl) methanol Analogs as PD-L1 Inhibitor
程序性死亡蛋白配体1抑制剂2-甲基-3-二苯基甲醇衍生物的定量结构活性关系研究
AbdullaAl Mamun，梅争，邱玲*，居学海*
Cancer is one of the most serious issues in human life. Blocking programmed cell death protein 1 and programmed death ligand-1 (PD-L1) pathway is one of the great innovations in the last few years, a few numbers of inhibitors can be able to block it. (2-Methyl-3-biphenylyl) methanol derivative is one of them. Here, the quantitative structure-activity relationship (QSAR) established twenty (2-methyl-3-biphenylyl) methanol derivatives as the programmed death ligand-1 inhibitors. Density functional theory at the B3LPY/6-31+G(d,p) level was employed to study the chemical structure and properties of the chosen compounds. Highest occupied molecular orbital energy EHOMO, lowest unoccupied molecular orbital energyEHOMO, total energy ET, dipole moment DM, absolute hardness η, absolute electronegativityχ, softness S, electrophilicity ω, energy gap ∆E, etc., were observed and determined. Principal component analysis (PCA), multiple linear regression (MLR) and multiple nonlinear regression (MNLR) analysis were carried out to establish the QSAR. The proposed quantitative models and interpreted outcomes of the compounds were based on statistical analysis. Statistical results of MLR and MNLR exhibited the coefficient R2 was 0.661 and 0.758, respectively. Leave-one-out cross-validation, r2m metric, r2m test, and “Golbraikh & Tropsha’s criteria” analyses were applied for the validation of MLR and MNLR, which indicate two models are statistically significant and well stable with data variation in the external validation towards PD-L1. The obtained results showed that the MNLR model predicts the bioactivity more accurately than MLR, and it may be helpful and supporting for evaluation of the biological activity of PD-L1 inhibitors.
Key words: Quantitative structure-activity relationship, 2-Methyl-3-biphenylyl methanol derivatives, Programmed death ligand-1 inhibitor, Density functional theory
DOI: 10.1063/1674-0068/cjcp1909168
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Multinanoparticle Translocations in Phospholipid Membranes: Translocation Modes and Dynamic Processes
多纳米粒子穿越磷脂膜
夏萍萍，单月，何林李，季永运，王向红，李士本*
Multinanoparticles interacting with the phospholipid membranes in solution were studied by dissipative particle dynamics simulation. The selected nanoparticles have spherical or cylindrical shapes, and they have various initial velocities in the dynamical processes. Several translocation modes are defined according to their characteristics in the dynamical processes, in which the phase diagrams are constructed based on the interaction strengths between the particles and membranes and the initial velocities of particles. Furthermore, several parameters, such as the system energy and radius of gyration, are investigated in the dynamical processes for the various translocation modes. Results elucidate the effects of multiparticles interacting with the membranes in the biological processes.
Key words: Multinanoparticle, Phospholipid membrane, Translocation mode, Dynamic process
DOI: 10.1063/1674-0068/cjcp1910174
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Bacterial Cellulose Templated p-Co3O4/n-ZnO Nanocomposite with Excellent VOCs Response Performance
细菌纤维素模板法制备p- Co3O4//n-ZnO复合材料及气敏特性研究
戚灵莉，钟春燕，邓赞红*，代甜甜，常鋆青，王时茂，方晓东，孟钢*
In this work, p-type Co3O4 decorated n-type ZnO (Co3O4/ZnO) nanocomposite was designed with the assistance of bacterial cellulose template. Phase composition, morphology and element distribution were investigated by XRD, SEM, HRTEM, EDS mapping and XPS. Volatile organic compounds (VOCs) sensing measurements indicated a noticeable improvement of response and decrease of working temperature for Co3O4/ZnO sensor, in comparison with pure ZnO, i.e., the response towards 100 ppm acetone was 63.7 (at a low working temperature of 180 ◦C), which was 26 times higher than pure ZnO (response of 2.3 at 240 ◦C). Excellent VOCs response characteristics could be ascribed to increased surface oxygen vacancy concentration (revealed by defect characterizations), catalytic activity of Co3O4 and the special p-n heterojunction structure, and bacterial cellulose provides a facile template for designing diverse functional heterojunctions for VOCs detection and other applications.
Key words: Bacterial cellulose, Heterojunction, Metal oxide composite, ZnO, Gas sensor
DOI: 10.1063/1674-0068/cjcp2003038
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Improving Interfacial Electrochemistry of LiNi0.5Mn1.5O4 Cathode Coated by Mn3O4
Mn3O4包覆对LiNi0.5Mn1.5O4正极材料界面电化学性能的提高
邓苗苗，张大伟，邵宇，贺晓东，Aqsa Yasmin，陈春华*
In this work the surface of LiNi0.5Mn1.5O4 (LMN) particles is modified by Mn3O4 coating through a simple wet grinding method, the electronic conductivity is significantly improved from 1.53×10−7 S/cm to 3.15×10−5 S/cm after 2.6 wt% Mn3O4 coating. The electrochemical test results indicate that Mn3O4 coating dramatically enhances both rate performance and cycling capability (at 55 oC) of LNM. Among the samples, 2.6 wt% Mn3O4-coated LNM not only exhibits excellent rate capability (a large capacity of 108 mAh/g at 10 C rate) but also shows 78% capacity retention at 55 oC and 1 C rate after 100 cycles.
Key words: Lithium-ion batteries, Cathode materials, Spinel lithium nickel manganese oxide, Surface modification, Cathode-electrolyte interphase
DOI: 10.1063/1674-0068/cjcp1906118
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In situ One-Pot Fabrication of MoO3-x Clusters Modified Polymer Carbon Nitride for Enhanced Photocatalytic Hydrogen Evolution
MoO3-x /PCN的原位合成及其增强光催化产氢性能的研究
戚荣杰，刘军营，韦之栋，郭伟琦，江治*，上官文峰
Developing low-cost and high-efficient noble-metal-free cocatalysts has been a challenge to achieve economic hydrogen production. In this work, molybdenum oxides (MoO3-x) were in situ loaded on polymer carbon nitride (PCN) via a simple one-pot impregnation-calcination approach. Different from post-impregnation method, intimate coupling interface between high-dispersed ultra-small MoO3-x nanocrystal and PCN was successfully formed during the in situ growth process. The MoO3-x-PCN-X (X=1, 2, 3, 4) photocatalyst without noble platinum (Pt) finally exhibited enhanced photocatalytic hydrogen performance under visible light irradiation (λ>420 nm), with the highest hydrogen evolution rate of 15.6 µmol/h, which was more than 3 times that of bulk PCN. Detailed structure-performance revealed that such improvement in visible-light hydrogen production activity originated from the intimate interfacial interaction between high-dispersed ultra-small MoO3-x nanocrystal and polymer carbon nitride as well as efficient charge carriers transfer brought by Schottky junction formed. Key words: Noble-metal-free cocatalyst, Polymer carbon nitride, MoO3-x clusters, Schottky junction, Photocatalytic hydrogen production
DOI: 10.1063/1674-0068/cjcp1912220
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Large-Scale Synthesis of Porous Bi2O3 with Oxygen Vacancies for Efficient Photodegradation of Methylene Blue
王利容，侯婷婷，辛月，竹文坤，余术宜*，谢子铖，梁叔全*，王梁炳*
Photocatalytic degradation of organic pollutants has become a hot research topic because of its low energy consumption and environmental-friendly characteristics. Bismuth oxide (Bi2O3) nanocrystals with a bandgap ranging from 2.0 eV to 2.8 eV have attracted increasing attention due to high activity of photodegradation of organic pollutants by utilizing visible light. Though several methods have been developed to prepare Bi2O3-based semiconductor materials over recent years, it is still difficult to prepare highly active Bi2O3 catalysts in large scale with a simple method. Therefore, developing simple and feasible methods for the preparation of Bi2O3 nanocrystals in large scale is important for the potential applications in industrial wastewater treatment. In this work, we successfully prepared porous Bi2O3in large scale via etching commercial BiSn powders, followed by thermal treatment with air. The acquired porous Bi2O3 exhibited excellent activity and stability in photocatalytic degradation of methylene blue. Further investigation of the mechanism witnessed that the suitable band structure of porous Bi2O3 allowed the generation of reactive oxygen species, such as O2−· and ·OH, which effectively degraded MB.
Key words: Bi2O3 photocatalyst, Photocatalytic degradation, Large scale, Visible light, Photocatalysis
DOI: 10.1063/1674-0068/cjcp2001009
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Chinese Journal of Chemical Physics是中国物理学会主办，中国科学技术大学和中国科学院大连化学物理研究所协办，中国科协主管的化学物理类综合性英文学术期刊。本刊创刊于1988年，创刊名为“化学物理学报”，双月刊，2006年起改为全英文刊。本刊办刊宗旨为“面向国际化学和物理学前沿领域，及时报道化学和物理学各领域中创新科研成果和最新进展，学术成果”。报道和刊登国内外化学物理学科各领域创新性成果的“研究论文”、“研究快讯”及“前沿研究综述”。本刊严格按照国际选稿原则和编辑规范，注重原创性和快速性。本刊从2006年1月起至2012年12月，与英国物理学会出版集团（IOPP）合作。2013年至今与美国物理联合会（AIP）合作，由AIP代理海外出版发行。本刊从2002年起被SCI等国际检索系统收录。自2008年以来本刊的影响因子一直在稳定提升，具体情况详细见SCI IF。
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