Photolysis Dynamics Laser Chemistry Lab

Polynorbornenes appended with anthracene and chiral alanine linkers are synthesized. Hydrogen bonding between the adjacent bisamidic linkers brings adjacent anthracene chromophores in a more suitable orientation for exciton coupling and renders one-handed helical structures for these polymers. Excimer formation is observed from their emission spectra. Monoamidic linkers provide only one hydrogen bond, which would be less robust and result in much lower circular dichroic response. Hydrogen bonding between the adjacent chiral alanine linkers brings appended anthracene in a more suitable orientation for exciton coupling and excimer formation, rendering one-handed helical structures in polynorbornenes. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous carbon nanosheets were prepared by the carbonization of paper flower via chemical and physical activation. The structural properties of the as-prepared carbons were characterized using the techniques, such as X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), Raman spectroscopy, N2 sorption isotherms and X-ray photoelectron spectroscopy (XPS), while the related morphological analyses were conducted using scanning/transmission electron microscopy (SEM/TEM). The obtained carbons exhibit a high specific surface area up to 1801 m2 g−1 with a robust porous graphitic carbon layer structure, which provides the merits for potential application in energy storage and dye removal. We carried out potentiostatic and galvanostatic measurements using a three-electrode cell in 1.0 M H2SO4 aqueous electrolyte and achieved a specific capacitance of 118, 109.5, 101.7, 93.6, and 91.2 F g−1 at 1, 2, 4, 8 and 12 A g−1, respectively. The stability at 12 A g−1 was tested to reach 10,000 cycles with capacity retention of around 97.4%. We have demonstrated that the paper flower-derived carbons at activation temperature 800 °C (PFC-800) can be used as a promising electrode material in supercapacitor. PFC-800 can also serve as an efficient sunset yellow dye removal, showing the maximum adsorption capacity for sunset yellow (Q0, 273.6 mg g−1). © 2018 King Saud University

Photodissociation of isobutyraldehyde (C3H7CHO) at 248 nm is investigated using time-resolved Fourier-transform infrared emission spectroscopy to demonstrate the growing importance of the roaming pathway with increasing molecular size of aliphatic aldehydes. Each acquired CO rotational distribution from v = 1 to 4 is well characterized by a single Boltzmann rotational temperature from 637 to 750 K, corresponding to an average rotational energy of 5.9 ± 0.6 kJ mol-1. The roaming signature that shows a small fraction of CO rotational energy disposal accompanied by a vibrationally hot C3H8 co-fragment is supported by theoretical prediction. The energy difference between the tight transition state (TS) and the roaming saddle point (SP) is found to be -27, 4, 15, 22, and 30 kJ mol-1 for formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, and 2,2-dimethyl propanal, respectively. The roaming SP is stabilized by a larger alkyl moiety. It is suggested that the roaming photodissociation rate of aldehydes increasingly exceeds those via the tight TS, resulting in the dominance of the CO + alkane products, as the size of aldehydes becomes larger. Along with formaldehyde, acetaldehyde, and propionaldehyde, in this work isobutyraldehyde is further demonstrated that this aldehyde family with special functional group is the first case in the organic compound to follow predominantly a roaming dissociation pathway, as the molecular size becomes larger. © the Owner Societies 2015.

The orientation dependence of Br-atom formation in the reaction of the oriented OH radical with the HBr molecule using the hexapole electrostatic field was studied. Experimental results for the orientation dependence in the reaction were analyzed using a Legendre polynomial fit. The results show two reactive sites. It was found that O-end attack is most favored for this reaction, and that H-end attack also shows a pronounced reactivity. The reactivity of the side-ways attack was found to be small. By comparing the results of the orientation dependence in the reaction with studies of inelastic collisions and theoretical calculations, two reaction pathways are proposed. Reaction by O-end attack is followed by a direct abstraction of the H-atom from the HBr molecule. The mechanism for H-end attack may have H-atom migration from HBr to form the water molecule. © 2011 the Owner Societies.

A new reaction scheme is proposed to account for roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions, where nonadiabatic dynamics plays a key role and the collapse of superposition of wave functions is considered to be important in the beginning of the present scheme. Since the feature of molecular orbitals of reagents is crucial in reaction, we showed how to map out the spatial distribution of the relevant HOMO molecular orbitals of CH3Cl in the impact of fast electrons. We identified by experiment that the multiple overlap of nearby molecular orbitals affects even the vibrational motion of adjacent molecule DCl of the transient [ClDCl] chemical species. We also showed dynamical steric effects in the HBr + OH four-atom reaction as a manifestation of the nonadiabatic dynamics in complex systems. The roaming mechanism in the photo-initiated reaction of methyl formate is clarified in detail by experiment as well as the QCT trajectory calculation, where the conical intersection region plays an essential role. We suggest that two types of roaming trajectories coexist, i.e., deterministic and chaotic roaming trajectories based on classical trajectory calculations. To clarify the nonadiabatic dynamics in the roaming mechanism for non-collinear three-dimensional (3D) collisions, a new model of the 3D Polanyi rule is proposed as the extension of the well-established 2D Polanyi rule. In the 3D Polanyi rule, it is expected that the curvature and torsion of Frenet–Serret formulas in three-dimensional space would provide us key concepts in understanding reaction dynamics. © 2018, Accademia Nazionale dei Lincei.

Without the need to construct complicated potential energy surfaces, a multicenter impulsive model is developed to characterize the dynamical feature of conventional transition state (TS) and roaming pathways in the photodissociation of formaldehyde, H2CO → CO + H2. The photofragment energy distributions (PED) resulting from the roaming mechanism are found to closely correlate to a particular configuration that lies close to the edge of the plateau-like intrinsic reaction coordinate, whereas such a PED is associated with the configuration at the saddle point when the conventional TS pathway is followed. The evaluated PED results are consistent with those by experimental findings and quasi-classical trajectory calculations. Following impulsive analysis, the roaming pathway can be viewed as a consequence of energy transfer events between several vibrational modes. For H2CO, the available energy initially accumulated at the C-H bond is transferred to other transitional mode(s) via stretching-bending coupling, and finally to the HH stretching. (Chemical Presented). © 2014 American Chemical Society.

In one-photon dissociation of propionyl chloride at 248 nm, time-resolved Fourier-transform infrared emission spectroscopy is used to detect the fragments of HCl and CO in the presence of Ar. The inert gas Ar plays a role to enhance the internal conversion. The time-dependence of high-resolution HCl spectra yields a bimodal rotational distribution in the early stage. The total rotational and vibrational energy partitioned in HCl are evaluated to be 1.7 ± 0.3 and 8.8 ± 1.9 kcal/mol, respectively. The CO appearance indicates that HCl may be eliminated through a five-center mechanism accompanied with three-body dissociation of C2H2, HCl, and CO. A four-center mechanism forming HCl and CH3CHCO also contributes to the HCl fragment with a feature of rotational bimodality. However, the probability for the HCl contribution from the hot Cl reaction is negligible. The reaction with CH4 is carried out to evaluate the HCl and Cl elimination rate constants. © 2010 Elsevier B.V. All rights reserved.

This perspective article aims at accounting for the versatility of some current experimental investigations for exploring novel paths in chemical reactions. It updates a previous one [Phys. Chem. Chem. Phys., 2005, 5, 291] and is limited to work by the authors. The use of advanced molecular beam techniques together with a combination of modern tools for specific preparation, selection and detection permits us to discover new trends in reactivity in the gas phase as well as at interfaces. We specifically discuss new facets of stereodynamics, namely the effects of molecular orientation and alignment on reactive and photodissociation processes. Further topics involve roaming paths and triple fragmentation in photodissociation probed by imaging techniques, chirality effects in collisions and deviations from Arrhenius behavior in the temperature dependence of chemical reactions. © the Partner Organisations 2014.

Palladium-copper nanoparticles were placed on activated carbon to give a nanocomposite for electrochemical sensing of riboflavin (vitamin B 2 ). The activated carbon was produced by pyrolysis of natural waste of pistachio nutshells after KOH activation and under a nitrogen atmosphere. The carbons possess a large surface area and micro/meso-porosity. The nanocomposite was characterized by a variety of techniques to confirm structures and morphology. A screen-printed electrode modified with the composite was examined by EIS, CV, DPV, and amperometry. The effects of pH value, scan rate, and stability of the modified electrode were studied. Under optimized conditions, vitamin B 2 displays a well-expressed oxidation peak at −0.15 V (vs. Ag/AgCl) in solutions with a pH value of 7.0. The voltammetric signal increases linearly in the 0.02 to 9 μM concentrations range and a lower detection limit of 7.6 pM. The sensor was successfully applied to the determination of vitamin B 2 even in the presence of other common vitamins and in (spiked) raw milk samples. [Figure not available: see fulltext.]. © 2019, Springer-Verlag GmbH Austria, part of Springer Nature.

A multi-center impulsive model has been recently developed to characterize the dynamic feature of product energy distribution in photodissociation of formaldehyde, H2CO → CO + H2. (J. Phys. Chem. A, 2015, 119, 29) The model is extended to predict the vector correlations among transition dipole moment μ of the parent molecule, recoil velocity v and rotational angular momentum j of the fragments produced via the transition state (TS) and roaming path. The correlation results of μ-j, j-j and μ-v vectors of the fragments are consistent with those reported using quasi-classical trajectory simulation on the global potential energy surface. In contrast to the TS route, the vector properties via the roaming path are loosely correlated. This work offers an alternative method to study stereodynamics of the photodissociation process, and is conducive to clarifying the origin of photofragment vector correlation especially for the roaming pathway. This journal is © the Owner Societies.

Ab initio potential energy surfaces and the corresponding analytical energy functions of the ground 1A′ and excited 2A′ states for the Li(22P) plus H2 reaction are constructed. Quasiclassical trajectory calculations on the fitted energy functions are performed to characterize the reactions of Li(22P) with H2(v 0, j 1) and H2(v 1, j 1) as well as the reaction when the vibrational energy is replaced by collision energy. For simplicity, the transition probability is assumed to be unity when the trajectories go through the crossing seam region and change to the lower surface. The calculated rotational distributions of LiH(v 0) for both H2(v 0, j 1) and H2(v 1, j 1) reactions are single-peaked with the maximum population at j′ 7, consistent with the previous observation. The vibrational excitation of H2(v 1) may enhance the reaction cross section of LiH(v′ 0) by about 200 times, as compared to a result of 93-107 reported in the experimental measurements. In contrast, the enhancement is 3.1, if the same amount of energy is deposited in the translational states. This endothermic reaction can be considered as an analog of late barrier. According to the trajectory analysis, the vibrational excitation enlarges the H-H distance in the entrance channel to facilitate the reaction, but the excess energy may not open up additional reaction configuration. © 2011 American Institute of Physics.

In this work, we describe a facile fabrication of silver nanoparticles decorated on porous ultrathin two dimensional (2D) graphitic carbon nitride nanosheets (AgNPs@g-CN) via chemical approach, which was characterized by various analytical techniques including cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. As expected, the AgNPs@g-CN modified glassy carbon electrode (AgNPs@g-CN/GCE) exhibited remarkable electrocatalytic activity towards the detection of quercetin (QCR) with a wide linear range from 1.0 × 10−8 to 1.2 × 10−4 mol L−1 and a lower detection limit of 6.0 × 10−9 mol L−1. Besides, the amperometric results revealed that the peak current for QCR could not affect upon the sequential additions of electroactive interfering species such as metal ions (300 μM), biomolecules (100 μM), and other flavonoids (50 μM) indicating the selectivity of the proposed sensor. Moreover, the AgNPs@g-CN modified electrode displayed higher stability and reproducibility towards the detection of QCR. The AgNPs@g-CN/GCE could also be used to detect QCR in green apple (GA) samples with satisfactory recoveries for practical applications. The concepts behind the novel architecture to modify electrodes can be potentially harnessed in other electrochemical sensors and photocatalysis applications. © 2018 Elsevier B.V.