Real‐Time Measurement of the Size Distribution of Diesel Exhaust Particles using a Portable 4‐stage Electrical Low Pressure Impactor

For this study, a 4 stage electrical low pressure impactor was designed to measure the real‐time size distribution of diesel particulate matter (DPM). For the performance evaluation, sodium chloride (NaCl) particles and dioctyl sebacate (DOS) particles were used. After evaluating the collection efficiency of each stage of the impactor, the size distributions of test particles were estimated using electrical current data and their inversion algorithm, and this was found to agree with the results obtained by a scanning mobility particle sizer (SMPS). For measurement of DPM, a common‐rail direct injection (CRDI) diesel engine, for engine speeds of 1,200 rpm and 1,500 rpm at 2.7 kgf·m, was used. Therefore, it was found that the size distribution of the DPM could be easily obtained, with the currents measured by the impactor and the data inversion algorithm, in less than 5 seconds. Furthermore, the effective density of the DPM could be obtained using the calculated results and the SMPS data.     

Simultaneously Probing Two Ultrafast Condensed‐Phase Molecular Symmetry Breaking Events by Two‐Dimensional Infrared Spectroscopy

In condensed phases, a highly symmetric gas‐phase molecule lowers its symmetry under perturbation of the solvent, which is vital to a variety of structural chemistry related processes. However, the dynamical aspects of solvent‐mediated symmetry‐breaking events remain largely unknown. Herein, direct evidence for two types of solvent‐mediated symmetry‐breaking events that coexist on the picosecond timescale in a highly symmetric anion, namely, hexacyanocobaltate, is presented: 1) an equilibrium symmetry‐breaking event in which a solvent‐bound species having lowered symmetry undergoes a population exchange reaction with the symmetry‐retaining species; 2) a dynamic symmetry‐breaking event that is composed of many dynamic population‐exchange reactions under fluctuating solvent interactions. Ultrafast two‐dimensional infrared spectroscopy is used to simultaneously observe and dynamically characterize these two events. This work opens a new window into molecular symmetry and structural dynamics under equilibrium and non‐equilibrium conditions.     

Theoretical Insights into Intermolecular Hydrogen-Bonding Strengthening in Fluorenone-Methanol Complexes Induced by Electronic Excitation and Bulk Solvent Effect

This work presents a theoretical insight into the variation of the site-specific intermolecular hydrogen-bonding （HB）, formed between C=O group of fluorenone （FN） and O-H groups of methanol （MeOL） molecules, induced by both the electronic excitation and the bulk solvent effect. Through the calculation of molecular ground- and excited-state properties, we not only demonstrate the characters of HB strengthening induced by electronic excitation and the bulk solvent effect but also reveal the underlying physical mechanism which leads to the HB variation. The strengthening of the intermolecular HB in electronically excited states and in liquid solution is characterized by the reduced HB bond-lengths and the red-shift IR spectra accompanied by the increasing intensities of IR absorption corresponding to the characteristic vibrational modes of the O-H and C--O stretching. The HB strengthening in the excited electronic states and in solution mainly arises from the charge redistribution of the FN molecule induced by the electronic excitation and bulk solvent instead of the intermolecular charge transfer. The charge redistribution of the solute molecule increases the partial dipole moment of FN molecule and the FN-MeOL intermolecular interaction, which subsequently leads to the HB strengthening. With the bulk solvent effect getting involved, the theoretical IR spectra of HBed FN-MeOL complexes agree much better with the experiments than those of gas-phase FN-MeOL dimer. All the calculations are carried out based on our developed analytical approaches for the first and second energy derivatives of excited electronic state within the time-dependent density functional theory.     

Pyrenoimidazole‐Based Deep‐Blue‐Emitting Materials: Optical,Electrochemical, and Electroluminescent Characteristics

A series of pyrenoimidazoles that contained various functional chromophores, such as anthracene, pyrene, triphenylamine, carbazole, and fluorene, were synthesized and characterized by optical, electrochemical, and theoretical studies. The absorption spectra of the dyes are dominated by electronic transitions that arise from the pyrenoimidazole core and the additional chromophore. All of the dyes exhibited blue‐light photoluminescence with moderate‐to‐high quantum efficiencies. They also displayed high thermal stability and their thermal‐decomposition temperatures fell within the range 462–512 °C; the highest decomposition temperature was recorded for a carbazole‐containing dye. The oxidation propensity of the dyes increased on the introduction of electron‐rich chromophores, such as triphenylamine or carbazole. The application of selected dyes that featured additional chromophores such as pyrene, carbazole, and triphenylamine as blue‐emissive dopants into multilayered organic light‐emitting diodes with a 4,4′‐bis(9H‐carbazol‐9‐yl)biphenyl (CBP) host was investigated. Devices that were based on triphenylamine‐ and carbazole‐containing dyes exhibited deep‐blue emission (CIE 0.157, 0.054 and 0.163, 0.041), whereas a device that was based on a pyrene‐containing dye showed a bright‐blue emission (CIE 0.156, 0.135).     

Determination of the electron density in methyl (±)‐(1S,2S,3R)‐2‐methyl‐1,3‐diphenylcyclopropanecarboxylate using refinements with X‐ray scattering factors from wavefunction calculations of the whole molecule

The molecule of the title compound, C₁₈H₁₈O₂, is a substituted cyclopropane ring. The electron density in this molecule has been determined by refining single‐crystal X‐ray data using scattering factors derived from quantum mechanical calculations. Topological analysis of the electron densities in the three cyclopropane C—C bonds was carried out. The results show the effects of this substitution on these C—C bonds.     

First-principles characterization of formate and carboxyl adsorption on stoichiometric CeO2(111) and CeO2(110) surfaces

Molecular adsorption of formate and carboxyl on stoichiometric CeO₂(111) and CeO₂(110) surfaces was studied using periodic density functional theory (DFT+U) calculations. Two distinguishable adsorption modes (strong and weak) of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO₂(110) surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO₂ surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters (U = 0, 5, and 7). However, the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes (<0.2 eV). The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.     

Intermolecular interactions of formic acid with benzene: Energy decomposition analyses with ab initio MP2 and double‐hybrid density functional computations

The intermolecular interactions of formic acid (HCOOH) with benzene (C₆H₆) have been investigated using localized molecular orbital energy decomposition analyses (LMO‐EDA) with ab initio MP2 and several double‐hybrid density functionals. The molecular geometries of five HCOOH…C₆H₆ complexes and corresponding benchmark total interaction energies at the CCSD(T)/CBS level are taken from literature (Zhao et al., J. Chem. Theory Comput. 2009, 5, 2726). According to the results of LMO‐EDA with the MP2 method, the dispersion energies are found to be as important as the electrostatic energies for the total interaction energies of the five HCOOH…C₆H₆ complexes. Based on LMO‐EDA with the double‐hybrid density functionals of B2PLYP, B2K‐PLYP, B2T‐PLYP, and B2GP‐PLYP computations, two new parameters for the framework of B2PLYP are extrapolated. These two new parameters are tested with other 10 complexes involving C₆H₆ (Crittenden, J. Phys. Chem. A 2009, 113, 1663), and they perform well on predicting the corresponding total interaction energies. Interestingly, these two new parameters for the framework of B2PLYP also perform well on the noncovalent complexation energies database (NCCE31/05) developed by Truhlar's group (Zhao and Truhlar, J. Phys. Chem. A 2005, 109, 5656). Therefore, these two new parameters appear to be suitable for investigating the noncovalent interactions, and they are denoted as B2N‐PLYP, where N stands for the noncovalent interaction. This study is expected to provide new insight into the derivation of double‐hybrid density functionals for studying the noncovalent interactions. © 2013 Wiley Periodicals, Inc.     

Comment on “Extending Hirshfeld‐I to bulk and periodic materials”

In recent years, several methods have been developed that partition the electron density among atoms using spherically symmetric atomic weights. D. E. P. Vanpoucke, P. Bultinck, and I. Van Driessche (J. Comput. Chem. 2012, doi: 10.1002/jcc.23088) recently reported a periodic implementation of the Hirshfeld‐I method that uses a combination of Becke‐style and uniform integration grids and modified atomic reference densities to compute net atomic charges in periodic materials. Herein, this method is discussed in the context of earlier periodic implementations of the Hirshfeld‐I method, the Iterated Stockholder Atoms method, and the density derived electrostatic and chemical method.     

Validity of Inorganic Nanosheets as an Efficient Planar Substituent To Enhance the Enantioselectivity of Transition‐Metal‐Catalyzed Asymmetric Synthesis

Effectively enhancing the enantioselectivity is a persistent challenge in heterogeneous asymmetric catalysis. Here, the validity of a layered double hydroxides (LDH) nanosheet as an efficient planar substituent to enhance the enantioselectivity has been investigated theoretically; first in vanadium‐catalyzed asymmetric epoxidation of allylic alcohols, and then in zinc‐catalyzed direct asymmetric aldol addition. The computational predication is further confirmed experimentally in zinc‐catalyzed direct asymmetric aldol addition by controlling the location of catalytic sites.