Shibo Cheng

Shandong University | SDU · School of Chemistry and Chemical Engineering

Direct experimental determination of precise electron affinities (EAs) of lanthanides is a longstanding challenge to experimentalists. Considerable debate exists in previous experiment and theory, hindering the complete understanding about the properties of the atomic anions. Herein, we report the first precise photoelectron imaging spectroscopy of...

Significance Superatom concept has been found to be promising in designing atomic clusters to mimic the chemistry of scarce or expensive elements. Also, longstanding interest and challenge exist in searching for suitable candidates to mimic the valuable properties of rare earth elements owing to their highly important application in modern technolo...

Metal clusters featuring closed supershells or aromatic character usually exhibit remarkably enhanced stability in their cluster series. However, not all stable clusters are subject to these fundamental constraints. Here, by employing photoelectron imaging spectroscopy and ab initio calculations, we present experimental and theoretical evidence on...

The concept of aromaticity has been advanced beyond the framework of organic chemistry, and multiple aromaticity (σ, π, and δ) has been observed to account for the highly symmetric structures or unusual stability of the clusters. In the present study, the electronic structures and chemical bonding of small monolanthanum boride clusters are investig...

The fluorescence and phosphorescence emission studies have been performed to understand the photochemistry of o-nitrobenzaldehyde in solution upon photoexcitation to the first excited singlet state (S(1)). The presence of an energy barrier in the S(1)-state hydrogen transfer potential energy surface is determined experimentally through the observed...

Three designed novel Ag n @C 18 (n = 4-6) complexes with enhanced NLO response. • Remarkable charge transfer (CT) from silver cluster to the C 18 ring. • Ag 6 @C 18 exhibits the highest first static hyperpolarizability. • The UV-Vis absorption spectra were simulated for C 18 and Ag n @C 18 (n = 4-6). A R T I C L E I N F O Keywords: Cyclo[18]carbon...

Designing superatoms with special structural and photoelectric properties is vital for the applications in multiple fields including condensed matter physics, nanomaterials science etc. In this study, the effects of an oriented external electric field (OEEF) on the geometry, electronic properties, photoelectron spectrum (PES), and nonlinear optical...

The intramolecular proton transfer (IPT) reaction potential energy surfaces (PESs) of N,N'-bis(salicylidene)-[2-(3',4'-diaminophenyl)benzthiazole] (BTS) in the S0 state and S1 state are constructed. It is found that the IPT reactions in the ground state hardly take place due to the high reaction energy barrier for single-proton (6.3 kcal/mol) and d...

Arsenic speciation analysis is important for pollution and health risk assessment. Surface-enhanced Raman Spectroscopy (SERS) is supposed to be a promising detection technology for arsenic species owing to the unique fingerprints. However, further application of SERS is hampered by its poor repeatability. Herein, the role of surface silver ions on...

Seeking and designing stable, high-efficiency, and economical bifunctional catalysts for the metal-air battery is challenging but of great significance towards the conversion and storage of renewable energy. In this study, based on first principles calculations, the oxygen evolution (OER) and oxygen reduction reaction (ORR) catalytic performance of...

The core of the surface-enhanced Raman spectroscopy (SERS)-based techniques for dynamic monitoring is to realize rapid and reversible adsorption. Herein, the integration technology of electro-enhanced adsorption, solid-phase microextraction, and surface-enhanced Raman spectroscopy (EE-SPME-SERS) was developed to obtain sensitive, ultrafast, and rev...

Although there are some proposed explanations for fluorescence enhancement of metal ions, a phenomenon with wide applications in biosensors and chemosensors, current understanding of the quantum-mechanical origin of this photophysical behaviour is limited. To address this issue, we selected thymolphthalein-based probe (T) reported recently as model...

Rationalizing a single-parameter descriptor that can conveniently and accurately evaluate the catalytic performance of single-atom catalysts (SACs) for oxygen evolution reaction (OER) is one of the most important and challenging goals in electrochemical energy applications. Herein, the OER processes for different SACs based on various mono-layer ma...

Developing highly efficient and economical bifunctional catalysts for overall water splitting is challenging but of great concern to renewable energy conversion and applied catalysis towards sustainable development. Herein, by employing...

Novel SERS substrates is urgently in demand for rapid and sensitive analysis of toxic agrochemicals from food. In this work, a monodispersed tungsten disulfide quantum dots modified silver nanosphere ([email protected]2QD) was prepared and used as SERS substrate. [email protected]2QD generated uniform and stable SERS signals within 2 min, displayin...

The singlet fission (SF) channels in many systems are controlled by the thermodynamic driving force (Switch-1) and kinetic barrier (Switch-2), both of which could be modulated by chromophore structure dynamics and solvent properties. Using ab initio molecular dynamics (AIMD), we here simulate how the structural dynamics and solvent jointly govern s...

The geometrical structures, aromatic character, and oriented external electric field (OEEF) regulated superhalogen formation of the neutral and charged AuSc2 clusters were explored by employing the density functional theory (DFT) calculations. The open-shell dual aromaticity involving the delocalization of d orbitals of transition metal atoms was e...

Carbonaceous shell-coated γ-Fe2O3 nanoparticles (γ-Fe2O3@CNM) were synthesized from glucose caramelization and used as a novel magnetic solid-phase extraction medium for malachite green and crystal violet in environmental water. Malachite green and crystal violet were absorbed on to γ-Fe2O3@CNM by electrostatic and π-interactions. The morphologies,...

We report a comprehensive theoretical study on the effect of the oriented external electric field (OEEF) on the geometrical structures and electronic properties of Ag19. The OEEF was confirmed to have the power in dramatically increasing the EA of Ag19 precisely and continuously while maintaining its geometry and energetic stability. Moreover, the...

By using the density functional theory calculations, two external fields, ligand field and the oriented external electric field (OEEF), were introduced to examine their capability in regulating electronic properties of the polymeric Nb2N2 cluster. The ligation strategy was observed to be able to dramatically lower the AIPs of the ligated Nb2N2 clus...

By employing the density functional theory calculations, we report a theoretical study about the geometrical and electronic structures of MnB6-1/0. Their ground states are planar featuring open-shell configurations. Additionally, the oriented external electric field (OEEF) was found to possess the capability in altering the electron affinity (EA) o...

Clathrate hydrates (CHs) have recently attracted considerable research interest in fundamental science and practical applications because guest molecules with special electronic properties can be selectively trapped in the hydrogen-bonded water cages, and thus such CHs could be a novel class of promising functional materials. However, information a...

Electrocatalytic hydrogen evolution reaction (HER) is essential for the future renewable and clean energy technology. Screening low-cost and highly active catalysts efficiently, however, is still a grand challenge. Herein, we symbolize a highly efficient guiding principle to govern the electrocatalytic activity of single-atom catalysts (SACs) based...

As a bridge between homogeneous and heterogeneous catalysis, single-atom catalysts (SACs), especially the noble metal atoms, have caught an extensive attention from both the fundamental and applied perspectives recently. High cost and difficulty in synthesis are considerable factors, however, limiting the development and practical applications of S...

Seeking novel strategies for designing superatoms is of significance for the potential applications in cluster-assembled nanomaterials. Herein, by employing the density functional theory (DFT) calculations, the effect of the oriented external electronic field (OEEF) on the electronic and photoelectron spectroscopic properties of the superatom-polym...

Conventional electronic rules, including Jellium and Wade-Mingos rules etc., have long been successfully dedicated to design superatoms. These rules, however, rely on altering the intrinsic properties, e.g. compositions or the number of valence electrons, of clusters, which is relatively complicated and inconvenient to manipulate, especially in exp...

With the help of computational chemistry tools, three non-fullerene acceptors, which are 2-methylene-malononitrile (M-1), 2-(3-methyl-5-methylene-2-thioxothiazolidin-4-ylidene) malononitrile (M-2) and 1-methyl-5-methylene-2,6-dioxo-1,2,5,6-tetrahydropyridine-3-carbonitrile (M-3), are designed with naphthalene diimide (NDI) central unit. Their diffe...

Seeking for novel superatoms with tunable electronic and magnetic properties has received numerous interests due to its potential application in the cluster assembly nanomaterials. By employing the density functional theory (DFT) calculations, recently observed superatomic WC cluster was adopted as the basic unit to construct larger polymeric clust...

Discovering the non-noble ZrO cluster as the analog of the noble metal catalyst Pd is of significance toward designing functional materials with fine-tuned properties using the superatom concept. The effect of gradually assembling the ZrO superatomic unit on the electronic structures and chemical bonding of larger ZrO-polymeric clusters, however, i...

Given the tremendous potential applications of excited state intramolecular proton transfer (ESIPT) systems, ESIPT molecules have received widespread attention. In this work, based on density functional theory (DFT) and time‐dependent DFT (TDDFT) methods, we theoretically study the excited state dynamical behaviors of salicyladazine (SA) molecules....

We perform a theoretical investigation about the excited state intramolecular proton transfer (ESIPT) reaction for a novel 2-(2-hydroxy-3,5-dimethyl-phenyl)-benzooxazole-5-carboxylicacid (HDPBC) system. The ultrafast excited state process is due to the low potential barrier, which should be the reason why only one fluorescence peak can be observed...

The NH-based excited-state intramolecular proton transfer process of 2-(2′-aminophenyl)benzothiazole (PBT-NH2) and its three derivatives have been explored by the time-dependent density functional theory (TD-DFT) method. The scanned potential energy curves reveal that the energy barriers of the first singlet excited state of the four compounds alon...

This work presents a systematic study of the conducting and optical properties of a family of aromatic diimides reported recently and discusses the influences of side-chain substitution on the reorganization energies, crystal packing, electronic couplings and charge injection barrier of 4,5,9,10-pyrenediimide (PyDI). Quantum-chemical calculations c...

Given that molecular excited state dynamical process plays important roles in designing and developing novel applications in recent years. In this work, based on density functional theory (DFT) and time‐dependent density functional theory (TDDFT) methods, we theoretically explored the novel (benzo[d]thiazol‐2‐yl)‐5‐(9H‐carbazol‐9‐yl)phenol (HBT‐Cz)...

The water solvent is a well-known solvating medium which can stabilize unstable species in bulky water or molecular clusters, but little is known about the solvating performance of the clathrate hydrate cages and changes of molecular properties of the solutes. In this work, on the basis of the experimentally observed clathrate hydrate structures, w...

The existence of abundant 4f electrons significantly increases the complexity and difficulty in precisely determining the geometric and electronic structures of the lanthanide oxide clusters. Herein, by combining the photoelectron imaging spectroscopy and density functional theory (DFT) calculations, the electronic structure of GdO was investigated...

We present an extensive density functional theory (DFT) calculations on the geometrical and electronic structures of the triatomic LaX2- (X=Al, Ga, In) clusters. Various trail structures and spin states have been attempted to determine the lowest-energy geometries of these La-doped metal clusters. The ground states of all three clusters are calcula...

Solvated electrons have been found to exist in various media which also exhibit more intriguing properties such as superconductivity, nonlinear optical response and so on. However, how they affect the nuclear spin properties have not been proved. This work presents the first detailed study on solvated-electron-triggered indirect nuclear spin-spin J...

The electronic structure of the diatomic VO anion was explored by combining the photoelectron-imaging spectroscopy and high-level theoretical calculations. The electron affinity (EA) of VO is determined to be 1.244 ± 0.025 eV from the vibrationally resolved photoelectron spectrum acquired at 532 nm. The anisotropy parameter (β) for the EA defined p...

In this gas-phase photoelectron spectroscopy study, we present the electron binding energy spectrum and photoelectron angular distributions of NbN− by the velocity-map imaging technique. The electron binding energy of NbN− is measured to be 1.42 ± 0.02 eV from the X band maximum which defines the 0-0 transition between ground states of anion and ne...

We present a joint photoelectron imaging spectroscopic and theoretical investigation on the triatomic ZrC2(-) anion. Vibrationally resolved spectrum was acquired at 532 nm photon energy. Electron affinity for the neutral ZrC2 cluster was determined to be 1.60 ± 0.07 eV. The CCSD(T) level of theory was used to explore the ground-state geometries and...

The electronic and structural properties of small monomagnesium oxide clusters, MgOx(-) and MgOx (x = 1-4), have been investigated using a synergistic approach combining photoelectron imaging spectroscopy and first principles electronic structure calculations. The adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of MgOx(-) clu...

Gas-phase spectroscopic studies have greatly enhanced our understanding of the electronic structure and chemical bonding in metal-nitrides and oxides as well as metal-halides. While photoelectron spectroscopy of negatively charged clusters is a useful technique, spectroscopic investigations concerning metal-nitrides are still scarce. To gain insigh...

Clusters can be used as building blocks for new materials. However, in order to form a bulk material with clusters, they should be chemically stable. This stability can be characterized by a closed-shell electronic configuration having a large HOMO-LUMO gap. Met-Cars, metal-carbon species composed of early transition metals bonded to carbon, are st...

Photodissociation dynamics of salicylic acid (SA) in the gas phase at different photolysis wavelengths (266, 315-317 nm) is investigated by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence (LIF) technique. At all the photolysis wavelengths it is found that the nascent OH radicals are produced mostly in a vi...

Photodissociation of p-aminobenzoic acid at 266 nm was investigated by probing the nascent OH photoproduct employing the laser-induced fluorescence technique. It was found that the nascent OH radical was vibrationally cold and its rotational state distribution conformed to be a Boltzmann behavior, characterized by a rotational temperature of 1040 ±...

The detailed theoretical investigation on the dissociation of n-butyl nitrite leading to OH has been performed using the G3B3 method in both the S0 and T1 states. The calculations reveal that there exist three main dissociative mechanisms, which are α-H, β-H and δ-H transfer mechanisms, respectively. Additionally, some complexes have been located i...

Photodissociation dynamics of o-nitrophenol in the gas phase at different photolysis wavelengths (361-390 nm) is investigated, and the nascent OH radical is observed by the single-photon laser-induced fluorescence technique. At all the photolysis wavelengths, the OH radicals are formed in vibrationally cold state (upsilon(")=0) and have similar rot...

New route to gas-phase OH.: UV photolysis of gaseous o-nitrobenzaldehyde forms OH radicals via the transformation into the ketene or o-nitrosobenzoic acid intermediate (see figure). The OH. product is monitored by single-photon laser-induced fluorescence (LIF). Photolysis of gaseous o-nitrobenzaldehyde (o-NBA) with selected different excitation wav...

Photodissociation dynamics of o-nitrobenzoic acid at 295 and 355 nm is studied by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence technique. At both of the photolysis wavelengths, the OH fragments are found to be vibrationally cold but have different rotational state distributions. Upon photolysis at 295 n...

Photodissociation dynamics of benzenesulfonic acid at 266nm was studied by probing the nascent OH photoproduct using the single-photon laser-induced fluorescence technique. Measurements on the nascent OH fragment revealed that it was produced vibrationally cold and its rotational state distribution was Boltzmann-like, characterized by a rotational...

Photodissociation dynamics of benzoic acid monomer (BAM) at different ultraviolet excitation wavelengths (280-295 nm) has been investigated. The nascent OH product state distributions were measured using the laser-induced fluorescence (LIF) technique. The rotational state distributions, the Lambda-doublet-state ratio, and spin-orbit state distribut...

Measurements of the nascent NO fragments from the photodissociation of gaseous n-butyl nitrite at 266nm were performed using the one-photon excited laser induced fluorescence technique. The rotational state distributions of the photofragment NO are found to be well characterized by a Gaussian distribution, which indicates that the photolysis proces...