Quasi-classical trajectory calculations are performed to study the stereodynamics of the H(~2S) + NH(a^1?) →H_2(X^1Σ_g^+) + N(~2D) reaction based on the first excited state NH_2(1~2A') potential energy surface reported by Li et al.[Li Y Q and Varandas A J C 2010 J. Phys. Chem. A 114 9644] for the first time. We observe the changes of differential cross-sections at different collision energies and different initial reagent rotational excitations. The influence of collision energy on the k–k' distribution can be attributed to a purely impulsive effect. Initial reagent rotational excitation transforms the reaction mechanism from insertion to abstraction. The effect of initial reagent rotational excitations on k–k' distribution can be explained by the rotational excitation enlarging the rotational rate of reagent NH in the entrance channel to reduce the probability of collision between incidence H atom and H atom of target molecular. We also investigate the changes of vector correlations and find that the rotational angular momentum vector j' of the product H_2 is not only aligned, but also oriented along the y axis. The alignment parameter, the disposal of total angular momentum and the reaction mechanism are all analyzed carefully to explain the polarization behavior of the product rotational angular moment.
The effects of isotopic variants on stereodynamic properties for the title reactions have been investigated using a quasi-classical trajectory method based on the first excited state NH2(12A) potential energy surface [Li Y Q and Varandas A J C 2010 J. Phys. Chem. A 114 9644]. The forward–backward symmetry scattering of the differential cross section can be observed, which demonstrates that all these reactions follow the insertion mechanism. Three angle distribution functions P(θr), P(φr), and P(θr, φr) with different collision energies and target molecules H2/D2/T2 are calculated. It is shown that the product rotational angular momentum is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The title reaction is mainly governed by the "in-plane" mechanism through the calculated distribution function P(θr, φr). The observable influences on the rotational polarization of the product by the isotopic substitution of H/D/T can be demonstrated.
We derive a general ionization rate formula for the system of diatomic molecules in the velocity gauge. A more concise expression of the photoionization rate in the tunnel region is obtained for the first time. Comparisons are made among the different versions of strong-field approximation. The numerical study shows that the ionization rate in the velocity gauge is underestimated by a few orders compared with that in the length gauge. Our simple formula of ionization rate may provide an insight into the ionization mechanism for the system of diatomic molecules.
This paper proposes a modified strong field approximation model for evaluating nondipole effects on the ionization of an atom in an intense laser field. The photoelectron longitudinal momentum distributions(PLMD) of a hydrogen-like atom exposed to a mid-infrared laser field is calculated. The theoretical results indicate an obvious asymmetry in the PLMD, and an offset of the PLMD peak appears in the opposite direction of the beam propagation due to nondipole effects. The peak offsets of the PLMD increased with the laser intensity, imposed by the initial state of the hydrogen-like atom.
The best optimal initial reactant state and collision energy for observing the stereodynamical vector properties of the title reaction in the ground electronic state X2A potential energy surface(PES) [Zanchet et al. 2006 J. Phys. Chem. A 110 12017] are theoretically predicted using the quasi-classical trajectory(QCT) method for the first time. The calculated results reveal that the smallest value of the rotational quantum number j, larger vibrational quantum number v, and the lower strength of collision energy should be selected for offering the most obvious picture about the stereodynamical vector properties. Polarization-dependent differential cross sections and the angular momentum alignment distribution, P(θr) and P(Φr) in the center-of-mass frame, are obtained to gain an insight into the alignment and orientation of the product molecules. The rotational angular momentum vector j of CO is aligned to be perpendicular to reagent relative velocity k. The product polarizations align along the y axis, pointing to the positive direction of the y axis. A new method is developed to investigate massive reactions with various initial states and to further study the vector properties of the fundamental reactions in detail.
We experimentally investigated remotely excited Raman optical activity(ROA)using propagating surface plasmons in chiral Ag nanowires.Using chiral fmoc-glycyl-glycine-OH(FGGO)molecules,we first studied the local surface plasmon-enhanced ROA.We found that the Raman intensity can be excited by left-and right-circularly polarized lights and that the circular intensity difference(CID)can be significantly enhanced.Second,by selecting vibrational modes with large Raman and ROA intensities that are not influenced by chemical enhancements,we studied remotely excited ROA imaging and the CID of FGGO molecules by propagating a plasmonic waveguide using Ag chiral nanostructures.When laser light was radiated on one of the Ag terminals,the measured CID of the FGG at the other terminal showed little change compared to the local excited CID.Meanwhile,when the laser light was radiated on the Ag nanowires(not on the terminals)and was coupled to the nearby nanoantenna,the CID of the ROA could be manipulated by altering the coupling angle between the Ag nanowires.To directly demonstrate the propagation of ROA along the nanowire and its remote detection,we also measured the remotely excited ROA spectra.Our experimental method has the potential to remotely determine the chirality of molecular structures and the absolute configuration or conformation of a chiral live cell.
Due to its amazing ability to manipulate light at the nanoscale,plasmonics has become one of the most interesting topics in the field of light–matter interaction.As a promising application of plasmonics,surface-enhanced Raman scattering(SERS)has been widely used in scientific investigations and material analysis.The large enhanced Raman signals are mainly caused by the extremely enhanced electromagnetic field that results from localized surface plasmon polaritons.Recently,a novel SERS technology called remote SERS has been reported,combining both localized surface plasmon polaritons and propagating surface plasmon polaritons(PSPPs,or called plasmonic waveguide),which may be found in prominent applications in special circumstances compared to traditional local SERS.In this article,we review the mechanism of remote SERS and its development since it was first reported in 2009.Various remote metal systems based on plasmonic waveguides,such as nanoparticle–nanowire systems,single nanowire systems,crossed nanowire systems and nanowire dimer systems,are introduced,and recent novel applications,such as sensors,plasmon-driven surface-catalyzed reactions and Raman optical activity,are also presented.Furthermore,studies of remote SERS in dielectric and organic systems based on dielectric waveguides remind us that this useful technology has additional,tremendous application prospects that have not been realized in metal systems.
Yingzhou HuangYurui FangZhenglong ZhangLing ZhuMengtao Sun
