Laser-induced NMR shift of a paramagnetic system

Perturbation theory on optical ac Stark effect is applied to study the NMR spectroscopy in paramagnetic systems. Application of the circularly or linearly polarized optical field would lead to shifts in the NMR lines, which is proportional to the laser intensity and the induced polarizability tensors by hyperfine interaction. The induced shift for 193Ir NMR spectrum of [IrBrg]2- is expected to be of the order of 1-10 Hz as resonance is approached with light intensity 10 W·cm-2. For the supersonic molecular beam samples 193IrC, the laser-induced NMR shift is estimated to be as large as 1-10 MHz near resonance.     

CORRELATION BETWEEN GLASS TRANSITION OF POLYMERS AND ENERGY OF ROTATIONAL ISOMERIZATION OF MOLECULAR CHAINS

It has been shown that the free volume fraction at T_g is not a universal parameter for linear polymers of different molecular structure. The reason is that the volume expansion at T_g is partially contributed from the change of the numbers of conformations of isolated molecular chains due to internal rotation. In this paper, glassy transformation was connected with internal rotation of isolated molecular chains, and the relationship between free volume fraction of polymers at T_g and energy e of rotational isomerization of isolated molecular chains was formulated, e=-k·T_g·In (△α·T_g/1-△α. T_g). The values of calculated from the above formula are in good agreement with those published in the literatures. Thus, the method described in this paper can be used to estimate a parameter for the flexibility of isolated molecular chains.7     

Theoretical study of determining orientation and alignment of symmetric top molecule using laser-induced fluorescence

General expressions used for extracting the orientation and alignment parameters of a symmetric top molecule from laser-induced fluorescence (LIF) intensity are derived by employing the density matrix approach. The molecular orientation and alignment are described by molecular state multipoles. Excitation and detection are circularly and linearly polarized lights, respectively. In general cases, the LIF intensity is a complex function of the initial molecular state multipoles, the dynamic factors and the excitation-detection geometrical factors. It contains a population, ten orientation and fourteen alignment multipoles. The problem of how to extract the initial molecular state multipoles from the resolved LIF intensity is discussed.     

The helicity of Raman scattered light:principles and applications in two-dimensional materials

Raman spectroscopy has been not only a technique for characterizing the composition and lattice structure of materials,but also a platform to explore the electron-photon and electron-phonon couplings.When excited by circularly polarized light,the Raman scattered light can carry a spin angular momentum±h,which adds a new degree of freedom to study the Raman scattering process.This review explains the principles of the helicity of Raman scattered light excited by circular polarization,and introduces the recent advances in the fundamentals and applications of helicity-resolved Raman scattering in two dimensional(2 D)materials,including the assignment of overlapped Raman modes,the characterization of exciton-phonon coupling and the application in chiral optics.We hope that this review will give a comprehensive understanding of the helicity selection rule in the Raman scattering process and inspire more exploration on the applications of the helicity of Raman scattered light.     

Molecular Axis Orientation in Charge Transfer Reactions Determined with a Reaction Microscope

Based on the reaction microscope at the institute of modern physics, the reaction mechanism in molecular ion-atom collisions is investigated experimentally. The features of this system is illustrated by a kinematically complete experhnent performed for the collision process. Using the so-called list-mode data recording technique and the coincidence measurement, the momentum vector of each fragment from the molecular ion were recorded event by event. The orientation of the molecular axis for H2^＋ dissociation reactions could be determined for each event in the off-line analysis. The measured orientation of the molecular ion is believed the same as the one at the instance of collision under axial recoil approximation. The polar angle resolution of the molecular orientation of ±8° was obtained.     

Microwaves spark emission spectroscopy for the analysis of cations:A simple form of atomic emission spectroscopy

A novel method for the cation analysis was investigated.The analysis is based on the sparking of the salts of metals in a microwave oven after placing in a graphite cell.The graphite cell absorbs microwaves and produces high temperature which converts the salt into light emitting species.The colour of light was found to dependent on the nature of cation,however,the intensity of the emitted light was found to be depending upon the form and shape of the graphite assembly in addition to the concentration of the salt.This communication presents explanation for all these observations and for the systematic and quantitative analysis using microwave spark emission technique.     

DISTRIBUTIONS OF TEMPERATURE, VELOCITY AND VISCOSITY AT SYMMETRICAL AXIS OF CYLINDRICAL PLUME IN EARTH'S MANTLE WITH VARIABLE VISCOSITY

The parameters at the symmetrical axis of a cylindrical plume characterize the strength of this plume and provide a boundary condition which must be given to investigate the structure of a plume. For Newtonian fluid with a temperature-and pressure-dependence viscosity, an asymptotical solution of hydrodynamic equations at the symmetrical axis of the plume is found in the present paper. The temperature, upward velocity and viscosity at the symmetrical axis have been obtained as functions of depth, The calculated results have been given for two typical sets of Newtonian rheological parameters. The results obtained show that the temperature distribution along the symmetrical axis is nearly independent of the theological parameters. The upward velocity at the symmetrical axis, however, is strongly dependent on the rheological parameters.     

Photochemical effect driven fluid behavior control in microscale pores and channels

Manipulating the fluid transport in the microscale pores and channels is playing a paramount role in the realization of the versatile functions of microfluidics. In recent years, using light to control the fluid behavior in the microchannels/pores has attracted many researchers’ attention due to the advantages of light such as non-contact stimulation, tunable excitation, high spatial and temporal resolution. With efforts, great achievements and progresses have been achieved for photochemical eff...     

High sensitive piezoelectric quartz crystal liquid density sensor

<正>We report for the first time a cleavage phenomenon in the resonant peak of a piezoelectric quartz crystal(PQC) in liquid phase.In the presence of a strong longitudinal wave effect,an additional resonant peak appears in the conductance-frequency curve.With gradually increasing liquid density,the additional peak moves from low to high frequency region then disappears.The frequency of the additional resonant peak is sensitive to the change in liquid density.The frequency shift of the additional peak is linear with the liquid density in a given range.For a 5 MHz PQC with a reflection distance of 16 mm for longitudinal wave,the sensitivity to liquid density is 2.61×10~6 Hz g~(-1) cm~3.The overlap between the primary resonant peak and the additional resonant peak causes a decrease in the intensity of the former and an increase in the intensity of the latter.In a combined impedance analysis method,the changes in surface mass loading,density and viscosity of the liquid were monitored simultaneously by a PQC sensor.     

Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions

Experimental and theoretical results for molecular-frame photoemission are presented for inner-valence shell photoionization of the CO molecule induced by linearly and circularly polarized light. The experimental recoil frame photoelectron angular distributions (RFPADs) obtained from dissociative photoionization measurements where the velocities of the ionic fragment and photoelectron were detected in coincidence, are compared to RFPADs computed using the multichannel Schwinger configuration interaction method. The formalism for including a finite lifetime of the predissociative ion state is presented for the case of general elliptically polarized light, to obtain the RFPAD rather than the molecular frame photoelectron angular distribution (MFPAD), which would be obtained with the assumption of instantaneous dissociation. We have considered photoionization of CO for the photon energies of 26.0 eV, 29.5 eV, and 32.5 eV. A comparison of experimental and theoretical RFPADs allows us to identify the ionic states detected in the experimental studies. In addition to previously identified states, we found evidence for the 2 (2)Δ state with an ionization potential of 25.3 eV and (2)Σ(+) states with ionization potentials near 32.5 eV. A comparison of the experimental and theoretical RFPADs permits us to estimate predissociative lifetimes of 0.25-1 ps for some of the ion states. Consideration of the MFPADs of a series of (2)Π ion states indicates the importance of inter-channel coupling at low photoelectron kinetic energy and the limitations of a single-channel analysis based on the corresponding Dyson orbitals.     

Molecular frame and recoil frame photoelectron angular distributions from dissociative photoionization of NO2

The authors report measured and computed molecular frame photoelectron angular distributions (MFPADs) and recoil frame photoelectron angular distributions (RFPADs) for the single photon ionization of the nonlinear molecule NO2 leading to the (1a2)-1 b 3A2 and (4a1)-1 3A1 states of NO2+. Experimentally, the RFPADs were obtained using the vector correlation approach applied to the dissociative photoionization (DPI) involving these molecular ionic states. The polar and azimuthal angle dependences of the photoelectron angular distributions are measured relative to the reference frame provided by the ion recoil axis and direction of polarization of the linearly polarized light. Experimental results are reported for the photon excitation energies hnu=14.4 and 22.0 eV. Theoretically the authors give expressions for both the MFPAD and the RFPAD. They show that the functional form in the recoil frame, where an average over the azimuthal dependence of the molecular fragments about the recoil direction is made, is identical to that they have earlier found for the DPI experiments performed on linear molecules. MFPADs were then computed using single-center expansion techniques within the fixed-nuclei frozen-core Hartree-Fock approximation. The computed cross sections for ionization to the (1a2)-1 b 3A2 state show a strong propensity for ionization with the polarization of the light perpendicular to the plane of the molecule, whereas the ionization to the (4a1)-1 3A1 state of the ion is of similar intensity for all orientations of the polarization of the light in the molecular frame. These qualitative features of the MFPAD are also evident in the RFPAD. The RFPAD for ionization leading to the (1a2)-1 b 3A2 state is strongly peaked in the perpendicular orientation, whereas the RFPAD for ionization leading to the (4a2)-1 3A1 state is much more nearly isotropic. Comparison between experimental and theoretical RFPADs indicates that the recoil angle for NO+ fragments is approximately 50 degrees relative to the symmetry axis of the initial C2v symmetry of the NO2 molecule in the ionization leading to the (1a2)-1 b 3A2 state and the recoil angle is approximately 120 degrees for the O+ fragment for ionization leading to the (4a1)-1 3A1 state.     

Dissociative photoionization of N(2)O in the region of the N(2)O(+)(B (2)Pi) state studied by ion-electron velocity vector correlation

Dissociative direct photoionization of the N2O(X 1Sigma+) linear molecule via the N2O+(B 2Pi) ionic state induced by linearly polarized synchrotron radiation P in the 18-22 eV photon energy range is investigated using the (VA+,Ve,P) vector correlation method, where VA+ is the nascent velocity vector of the NO+, N2+, or O+ ionic fragment and Ve that of the photoelectron. The DPI processes are identified by the ion-electron kinetic energy correlation, and the IchiA+(thetae,phie) molecular frame photoelectron angular distributions (MFPADs) are reported for the dominant reaction leading to NO+ (X 1Sigma+,v) + N(2D)+ e. The measured MFPADs are found in satisfactory agreement with the reported multichannel Schwinger configuration interaction calculations, when bending of the N2O+(B 2Pi) molecular ion prior to dissociation is taken into account. A significant evolution of the electron scattering anisotropies is observed, in particular in the azimuthal dependence of the MFPADs, characteristic of a photoionization transition between a neutral state of Sigma symmetry and an ionic state of Pi symmetry. This interpretation is supported by a simple model describing the photoionization transition by the coherent superposition of two ssigma and ddelta partial waves and the associated Coulomb phases.     

Molecular frame photoelectron angular distributions for H2 ionization by single and trains of attosecond XUV laser pulses

The delayed autoionization of H₂ doubly excited states into channels of different inversion symmetry gerade and ungerade is investigated by using pulses of attosecond duration (isolated or packed in trains), linearly polarized along the molecular axis. It has been shown in previous work, by using XUV laser pulses with durations of 4 fs or longer, that the molecular frame photoelectron angular distributions (MFPAD) associated with the dissociative channel H⁺ + H(n?) are not symmetric with respect to the inversion center of the molecule. In contrast, the MFPADs become symmetric for shorter fs pulses. Here we show that, although this is still the case for pulses of attosecond duration, the combination of two of these pulses with a controlled time delay may still lead to asymmetric MFPADs. From the analysis of the time evolution of the calculated MFPADs, we propose a way to elucidate autoionization lifetimes of molecular resonant states. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2462–2471, 2010     

Photoelectron circular dichroism in core level ionization of randomly oriented pure enantiomers of the chiral molecule camphor

The inner-shell photoionization of unoriented camphor molecules by circularly polarized light has been investigated from threshold to a photoelectron kinetic energy of approximately 65 eV. Photoelectron spectra of the carbonyl C 1s orbital, recorded at the magic angle of 54.7 degrees with respect to the light propagation direction, show an asymmetry of up to 6% on change of either the photon helicity or molecular enantiomer. These observations reveal a circular dichroism in the angle resolved emission with an asymmetry between forward and backward scattering (i.e., 0 degrees and 180 degrees to the light beam) which can exceed 12%. Since the initial state is an atomiclike spherically symmetric orbital, this strongly suggests that the asymmetry is caused by final-state effects dependent on the chiral geometry of the molecule. These findings are confirmed by electron multiple scattering calculations of the photoionization dynamics in the electric-dipole approximation.     

Circular dichroism in the angle-resolved C 1s photoemission spectra of gas-phase carvone enantiomers

The inner-shell C 1s photoionization of randomly oriented molecules of the chiral compound carvone has been investigated using circularly polarized synchrotron radiation up to 30 eV above threshold. Binding energies of the C=O and CH2= carbon 1s orbitals were determined to be 292.8+/-0.2 and 289.8+/-0.2 eV, respectively. The remaining C-H C 1s levels substantially overlap under an intense central peak centered at 290.5+/-0.2 eV. The angle-resolved photoemission from the carbonyl carbon C=O core orbital in pure carvone enantiomers shows a pronounced circular dichroism of approximately 6% at the magic angle of 54.7 degrees to the light beam propagation direction. This corresponds to an expected 0 degrees -180 degrees forward-backward electron emission asymmetry of approximately 10%. On changing between the R and S enantiomers of carvone the sense or sign of the asymmetry and associated dichroism effectively reverses. The observed circular dichroism, and its energy dependence, is well accounted for by calculations performed in the pure electric dipole approximation.     

Photoelectron spectroscopy of above-threshold ionization of xenon with circularly and linearly polarized light

Above-threshold multiphoton ionization (photon energy 1.17 eV and 2.33 eV) of xenon was studied with circularly and linearly polarized light. Pronounced differences in shape have been observed for photoelectron spectra taken with linearly and circularly polarized light. With circularly polarized light a strong suppression of low-energy electrons was observed; the total electron yield was reduced by factors of approximately 4 (photon energy 2.33 eV) and, depending on the laser intensity, between 13 and 80 (photon energy 1.17 eV).     

Discrimination of Excited States of Acetylacetone through Theoretical Molecular-Frame Photoelectron Angular Distributions

Photoelectron angular distribution (PAD) in the laboratory frame for randomly oriented molecules is typically described by a single anisotropy parameter, the so-called asymmetry parameter. However, especially from a theoretical perspective, it is more natural to consider molecular photoionization by using a molecular frame. The molecular frame PADs (MFPADs) may be used to extract information about the electronic structure of the system studied. In the last decade, significant experimental efforts have been directed to MFPAD measurements. MFPADs are highly characterizing signatures of the final ionic states. In particular, they are very sensitive to the nature of the final state, which is embodied in the corresponding Dyson orbital. In our previous work on acetylacetone, a prototype system for studying intra-molecular hydrogen bond interactions, we followed the dynamics of the excited states involved in the photoexcitation–deexcitation process of this molecule. It remains to be explored the possibility of discriminating between different excited states through the MFPAD profiles. The calculation of MFPADs to differentiate excited states can pave the way to the possibility of a clear discrimination for all the cases where the recognition of excited states is otherwise intricate.     

Photoabsorption and S 2p photoionization of the SF6 molecule: resonances in the excitation energy range of 200-280 eV

Photoabsorption and S 2p photoionization of the SF(6) molecule have been studied experimentally and theoretically in the excitation energy range up to 100 eV above the S 2p ionization potentials. In addition to the well-known 2t(2g) and 4e(g) shape resonances, the spin-orbit-resolved S 2p photoionization cross sections display two weak resonances between 200 and 210 eV, a wide resonance around 217 eV, a Fano-type resonance around 240 eV, and a second wide resonance around 260 eV. Calculations based on time-dependent density functional theory allow us to assign the 217-eV and 260-eV features to the shape resonances in S 2p photoionization. The Fano resonance is caused by the interference between the direct S 2p photoionization channel and the resonant channel that results from the participator decay of the S 2s(-1)6t(1u) excited state. The weak resonances below 210-eV photon energy, not predicted by theory, are tentatively suggested to originate from the coupling between S 2p shake-up photoionization and S 2p single-hole photoionization. The experimental and calculated angular anisotropy parameters for S 2p photoionization are in good agreement.     

Enhancement of anthracene fragmentation by circularly polarized intense femtosecond laser pulse

The authors compared circularly and linearly polarized lights in the ionization and fragmentation of anthracene, using 800 nm femtosecond laser pulses at intensities of 10(13)-10(15) W cm-2. Singly and doubly charged intact molecular ions as well as numerous fragment ions were observed in the mass spectra, which were investigated as a function of laser intensity and polarization. At comparable intensities above the saturation threshold for complete ionization, the fragmentation pathways are enhanced with a circularly polarized field compared to a linearly polarized field. Resonant excitation of the molecular cation through the 2Au<--2Bg transition is proposed to be the initial step to ion fragmentation. The circularly polarized field interacts with a larger fraction of the randomly oriented molecules than the linearly polarized field, and this is considered to be the reason for the enhanced fragmentation brought about by circularly polarized light.