Insights into a Low-Rank Naomaohu Coal Structural Information by Multistage Fractions Coupled with LIAD-VUVPI-TOFMS.

In-depth insights into the chemical composition and structural information of coal are an effective way to improve the efficiency of coal utilization. Laser-induced acoustic desorption coupling with vacuum ultraviolet photoionization time-of-flight mass spectrometry (LIAD-VUVPI-TOFMS) was applied to structural characterization of cyclohexane extracts of low-rank Naomaohu coal. The characterization of four types (12 model compounds) of mixed coal model compounds (three compounds per category)-saturated hydrocarbons, substitute aromatic hydrocarbons, aromatic hydrocarbons, and aromatic heteroatom rings-demonstrated that the approach can provide intact molecular weight information. The cyclohexanone extract (E CYC) was obtained by microwave-assisted extraction and separated into four group components (F1-4) by column chromatography to achieve component classification and simplify analysis. The molecular weight and structure were obtained by LIAD-VUVPI-TOFMS and synchronous fluorescence spectroscopy, combined with microwave-assisted extraction and column chromatography to separate product characteristics. Chemical components of a total of 248 species were observed, of which 46 are derived from aliphatic hydrocarbons embedded in the coal skeleton structure, 132 species are derived from aromatic hydrocarbons embedded in the coal skeleton structure, 61 are derived from possible coal skeleton units (compounds have obvious stacking and bonding effects), and 9 could not be determined (aromatic hydrocarbons or a possible coal skeleton structure unit).

Deciphering the Superatomic Behavior of Group V Metal Monoxides.

The valence orbitals of Group V metal monoxides exhibit atomic-like properties which mimic that of coinage metal element atoms. The electronic structures of MO-1/0 (M = V, Nb, and Ta) have been determined by negative ion photoelectron velocity map imaging. Electron affinities and vibrational frequencies for the ground state and excited states of MO (M = V, Nb, and Ta) molecules have been identified as well as photoelectron angular distributions. On the basis of the equivalent-electron principle, MO- (M = V, Nb, and Ta) molecules bear valence electron configurations similar to those of coinage metal elemental atoms, despite having more complicated electronic states for molecules, and concomitant mimicry of magnetic superatom. Generally, other than low-spin states of coinage metal atoms, Group V metal monoxides demonstrate a high-spin state except for TaO, possessing the potential applications to inexpensive superatoms in industrial catalysis.

Development of a miniature time-of-flight mass spectrometer coupled with an improved substrate-enhanced laser-induced acoustic desorption source (SE-LIAD/TOF-MS).

A novel, compact and sensitive SE-LIAD/TOF-MS has been described. It facilitates fast sample preparation, and a full mass spectrum is acquired efficiently and sensitively. More importantly, it features the detection of non-acidic and non-basic or non-polar species, which is not suitable for determination by ESI and MALDI techniques. In this technique, standard samples, carbazole and melamine, are prepared on a Ti foil with a quartz plate attached to the backside of the Ti foil to perform a laser-induced acoustic desorption experiment (SE-LIAD) coupled to TOF-MS for analysis. Enhanced signals are observed with about 5.6 to 13.8 times higher than that obtained in the standard LIAD method, dependent on different ionization techniques. Compared to the EI spectra, the PI spectra for both species show intact and sharp molecular peaks. The limits of detection (LOD) of melamine were evaluated experimentally in the range from ∼2-6 pg (EI/MS mode) to ∼0.3-0.5 ng (VUV-SPI/MS mode). Thus, the method in this study exhibits rapid qualitative and quantitative analysis with good sensitivity, being free of the complex matrix influences.

Probing the geometric and electronic structures of the lanthanide oxide HoOn-1/0 (n = 1-3) clusters.

The complex 4f and 5d orbits of lanthanide oxide clusters increases the complexity and difficulty in both theoretical and experimental research. Combining the photoelectron imaging spectroscopy and ab initio calculations, the structural and electronic properties of HoO- were studied. The adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of HoO- have been measured to be 1.31(3) eV and 1.42(2) eV, respectively. To determine the vibrational structure and observed spectral bands in the photoelectron spectrum, Franck-Condon simulation of the ground-state transition for HoO- has been performed. The fundamental frequency of ground-state HoO is estimated to be 893 ± 73 cm-1. Density functional method (DFT) was used to study the neutral and anionic clusters of HoOn-1/0 (n = 1-3), and the most stable cluster structures were obtained. Based on the DFT calculations, the theoretical ADEs and VDEs of anionic HoOn- (n = 1-3) clusters were obtained and the photoelectron spectra (PES) of HoOn- (n = 1-3) clusters were simulated, which might stimulate further experimental investigations on the Ho oxide clusters. In addition, the corresponding molecular orbitals (MOs) were also discussed to reveal the interaction between Ho and O atoms. This study can help us to understand the chemical bonding in Ho-containing molecules and will provide some light in their surface chemistry and photochemistry investigation.

Aromaticity Criterion Is Not the Only Factor to Decide the Ring Stability of Boron Oxide Families: c-M2O2-/0 Clusters (M = B, Al, Ga, and In).

Generally, compared to conjugated chain molecules, aromaticity provides additional stability for the cyclic, planar, and conjugated molecules. Thus, the concept of aromaticity was undeniably utilized to explain the unique stability for extensive cyclic molecules (notably for benzene, recently reported boron rings, and all-metal multiply aromatic Al42- salts) to guide chemical syntheses. However, can aromaticity alone describe the stability for all of those cyclic and planar clusters or molecules? In this regard, we observed the four-membered prototypical rings: c-M2O2-/0 clusters (M = B, Al, Ga, and In) possessing unique rhombic (four-center, four-electron) π and σ o-bonds, which are considered to have 3-fold aromaticity. Moreover, we not only elucidated the key role of ring strain energy (RSE) to determine the stability of these rings but also unexpectedly revealed that the electrostatic interaction (ionicity) plays a fundamental role in the stability of Al2O2-/0 clusters through systematically experimental and theoretical investigations into the isolated M2O2-/0 clusters (M = B, Al, Ga, and In). Detailed geometries, molecular orbital, and chemical bonding nature were analyzed to unravel those influences. This work provides a clue in which RSE and the electrostatic effect should be carefully taken into account for the stability of diverse cyclic clusters or molecules compared to the expected stability factor from aromaticity.

The photoelectron-imaging spectroscopic study and chemical bonding analysis of VO2 -, NbO2 - and TaO2.

The transition-metal di-oxides, namely VO2 -, NbO2 - and TaO2 - have been studied using photoelectron velocity map imaging (PE-VMI) in combination with theoretical calculations. The adiabatic electron affinities of VO2 -, NbO2 - and TaO2 - are confirmed to be 2.029(8), 1.901(10) and 2.415(8) eV, respectively. By combining Franck-Condon (FC) simulation with theoretical calculations, the vibrational feature related to Nb-O and Ta-O stretching modes for the ground state has been unveiled. The photoelectron angular distribution (PAD) for VO2 -, NbO2 - and TaO2 - is correlated to the photo-detachment of the highest occupied molecular orbitals (HOMOs), which primarily gets involved in s- and d-orbitals of the V, Nb and Ta atoms. A variety of theoretical calculations have been used to analyze the chemical bonding features of VO2 -1/0, NbO2 -1/0 and TaO2 -1/0, which show that the strong M-O (M = V, Nb and Ta) bond is mainly characterized as ionicity.

Does gold behaves as hydrogen? A joint theoretical and experimental study.

It has been established that the noble-metal-H analogue has been found in a large number of noble-metal-ligand clusters in view of geometric and electronic structures. Here, we demonstrated a different view of noble-metal-H analogue between noble-metal and hydrogen in M(SCH3)2 - (M = Cu, Ag, Au and H) systems. Although H(SCH3)2 - is a typical ion-hydrogen bonding cluster dramatically different from the chemical bonding clusters of M(SCH3)2 - (M = Cu, Ag and Au), the comparison of the two typical bonding patterns has not yet been fully investigated. Through a series of chemical bonding analyses, it is indicated that the evolution has been exhibited from typical ionic bonding in Cu(SCH3)2 - to a significant covalent bonding nature in Au(SCH3)2 - and hydrogen bonding dominating in H(SCH3)2 -. The comparison of M(SCH3)2 - (M = Cu, Ag and Au) with H(SCH3)2 - illustrates the differences in bonding between noble metals and hydrogen, which are mainly related to their diverse atomic orbitals participating in chemical bonding.