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We introduce some simulation and experiment results of the multichannel magnetic stimulator development that has been carried out as an initial attempt to realize a multichannel functional magnetic stimulator. For efficient functional magnetic stimulations, precise spatial localization of stimulation sites without any movements of the stimulation coils is very important. We have found that the mutual coupling effect among the adjacent stimulation coils in the coil array has to be considered in the determination of the charge voltages in some coil array configurations. Experimental results obtained with a 4-channel magnetic stimulator are presented. Index Terms--Functional magnetic stimulation, multichannel, mutual coupling, stimulation coil.

The [H.sub.3][O.sup.-] anion has stable and metastable structures that resemble configurations in the vicinity of the transition state for the neutral reactions OH + [H.sub.2] [left and right arrow] [H.sub.2]O + H. Photoelectron spectroscopy of this anion probes the neutral reaction dynamics in the critical transition-state region. Accurate quantum dynamics calculations of the photoelectron intensity and photodissociation product energies are shown to provide a quantitatively reliable means of interpreting such experimental observations and reveal a detailed picture of the reaction dynamics.

Femtosecond stimulated Raman spectroscopy (FSRS) on the Stokes side arises from a third order polarization, P(3)(t), which is given by an overlap of a first order wave packet,|Ψ2(1)(pu,t)〉,prepared by a narrow band (ps) Raman pump pulse, Epu(t), on the upper electronic e2 potential energy surface (PES), with a second order wave packet,〈Ψ1(2)(pr*,pu,t),|that is prepared on the lower electronic e1 PES by a broadband (fs) probe pulse, Epr(t), acting on the first-order wave packet. In off-resonant FSRS,|Ψ2(1)(pu,t)〉 resembles the zeroth order wave packet |Ψ1(0)(t)〉 on the lower PES spatially, but with a force on |Ψ2(1)(pu,t)〉 along the coordinates of the reporter modes due to displacements in the equilibrium position, so that 〈Ψ1(2)(pr*,pu,t),| will oscillate along those coordinates thus giving rise to similar oscillations in P(3)(t) with the frequencies of the reporter modes. So, by recovering P(3)(t) from the FSRS spectrum, we are able to deduce information on the time-dependent quantum-mechanical wave packet averaged frequencies, ωj(t), of the reporter modes j along the trajectory of |Ψ1(0)(t)〉. The observable FSRS Raman gain is related to the imaginary part of P(3)(ω). The imaginary and real parts of P(3)(ω) are related by the Kramers-Kronig relation. Hence, from the FSRS Raman gain, we can obtain the complex P(3)(ω), whose Fourier transform then gives us the complex P(3)(t) to analyze for ω j(t). We apply the theory, first, to a two-dimensional model system with one conformational mode of low frequency and one reporter vibrational mode of higher frequency with good results, and then we apply it to the time-resolved FSRS spectra of the cis-trans isomerization of retinal in rhodopsin [P. Kukura et al., Science 310, 1006 (2005)]. We obtain the vibrational frequency up-shift time constants for the C12-H wagging mode at 216 fs and for the C10-H wagging mode at 161 fs which are larger than for the C11-H wagging mode at 127 fs, i.e., the C11-H wagging mode arrives at its final frequency while the C12-H and C10-H wagging modes are still up-shifting to their final values, agreeing with the findings of Yan et al. [ABSTRACT FROM AUTHOR]

Abstract Background Despite its superb lateral resolution, flat-panel-detector (FPD) based tomosynthesis suffers from low contrast and inter-plane artifacts caused by incomplete cancellation of the projection components stemming from outside the focal plane. The incomplete cancellation of the projection components, mostly due to the limited scan angle in the conventional tomosynthesis scan geometry, often makes the image contrast too low to differentiate the malignant tissues from the background tissues with confidence. Methods In this paper, we propose a new method to suppress the inter-plane artifacts in FPD-based tomosynthesis. If 3D whole volume CT images are available before the tomosynthesis scan, the CT image data can be incorporated into the tomosynthesis image reconstruction to suppress the inter-plane artifacts, hence, improving the image contrast. In the proposed technique, the projection components stemming from outside the region-of-interest (ROI) are subtracted from the measured tomosynthesis projection data to suppress the inter-plane artifacts. The projection components stemming from outside the ROI are calculated from the 3D whole volume CT images which usually have lower lateral resolution than the tomosynthesis images. The tomosynthesis images are reconstructed from the subtracted projection data which account for the x-ray attenuation through the ROI. After verifying the proposed method by simulation, we have performed both CT scan and tomosynthesis scan on a phantom and a sacrificed rat using a FPD-based micro-CT. Results We have measured contrast-to-noise ratio (CNR) from the tomosynthesis images which is an indicator of the residual inter-plane artifacts on the focal-plane image. In both cases of the simulation and experimental imaging studies of the contrast evaluating phantom, CNRs have been significantly improved by the proposed method. In the rat imaging also, we have observed better visual contrast from the tomosynthesis images reconstructed by the proposed method. Conclusions The proposed tomosynthesis technique can improve image contrast with aids of 3D whole volume CT images. Even though local tomosynthesis needs extra 3D CT scanning, it may find clinical applications in special situations in which extra 3D CT scan is already available or allowed.

Abstract Background Ring artifacts are the concentric rings superimposed on the tomographic images often caused by the defective and insufficient calibrated detector elements as well as by the damaged scintillator crystals of the flat panel detector. It may be also generated by objects attenuating X-rays very differently in different projection direction. Ring artifact reduction techniques so far reported in the literature can be broadly classified into two groups. One category of the approaches is based on the sinogram processing also known as the pre-processing techniques and the other category of techniques perform processing on the 2-D reconstructed images, recognized as the post-processing techniques in the literature. The strength and weakness of these categories of approaches are yet to be explored from a common platform. Method In this paper, a comparative study of the two categories of ring artifact reduction techniques basically designed for the multi-slice CT instruments is presented from a common platform. For comparison, two representative algorithms from each of the two categories are selected from the published literature. A very recently reported state-of-the-art sinogram domain ring artifact correction method that classifies the ring artifacts according to their strength and then corrects the artifacts using class adaptive correction schemes is also included in this comparative study. The first sinogram domain correction method uses a wavelet based technique to detect the corrupted pixels and then using a simple linear interpolation technique estimates the responses of the bad pixels. The second sinogram based correction method performs all the filtering operations in the transform domain, i.e., in the wavelet and Fourier domain. On the other hand, the two post-processing based correction techniques actually operate on the polar transform domain of the reconstructed CT images. The first method extracts the ring artifact template vector using a homogeneity test and then corrects the CT images by subtracting the artifact template vector from the uncorrected images. The second post-processing based correction technique performs median and mean filtering on the reconstructed images to produce the corrected images. Results The performances of the comparing algorithms have been tested by using both quantitative and perceptual measures. For quantitative analysis, two different numerical performance indices are chosen. On the other hand, different types of artifact patterns, e.g., single/band ring, artifacts from defective and mis-calibrated detector elements, rings in highly structural object and also in hard object, rings from different flat-panel detectors are analyzed to perceptually investigate the strength and weakness of the five methods. An investigation has been also carried out to compare the efficacy of these algorithms in correcting the volume images from a cone beam CT with the parameters determined from one particular slice. Finally, the capability of each correction technique in retaining the image information (e.g., small object at the iso-center) accurately in the corrected CT image has been also tested. Conclusions The results show that the performances of the algorithms are limited and none is fully suitable for correcting different types of ring artifacts without introducing processing distortion to the image structure. To achieve the diagnostic quality of the corrected slices a combination of the two approaches (sinogram- and post-processing) can be used. Also the comparing methods are not suitable for correcting the volume images from a cone beam flat-panel detector based CT.

Abstract Background Ventricular tachycardia (VT) and ventricular fibrillation (VF) are the most serious cardiac arrhythmias that require quick and accurate detection to save lives. Automated external defibrillators (AEDs) have been developed to recognize these severe cardiac arrhythmias using complex algorithms inside it and determine if an electric shock should in fact be delivered to reset the cardiac rhythm and restore spontaneous circulation. Improving AED safety and efficacy by devising new algorithms which can more accurately distinguish shockable from non-shockable rhythms is a requirement of the present-day because of their uses in public places. Method In this paper, we propose a sequential detection algorithm to separate these severe cardiac pathologies from other arrhythmias based on the mean absolute value of the signal, certain low-order intrinsic mode functions (IMFs) of the Empirical Mode Decomposition (EMD) analysis of the signal and a heart rate determination technique. First, we propose a direct waveform quantification based approach to separate VT plus VF from other arrhythmias. The quantification of the electrocardiographic waveforms is made by calculating the mean absolute value of the signal, called the mean signal strength. Then we use the IMFs, which have higher degree of similarity with the VF in comparison to VT, to separate VF from VTVF signals. At the last stage, a simple rate determination technique is used to calculate the heart rate of VT signals and the amplitude of the VF signals is measured to separate the coarse VF from VF. After these three stages of sequential detection procedure, we recognize the two components of shockable rhythms separately. Results The efficacy of the proposed algorithm has been verified and compared with other existing algorithms, e.g., HILB 1, PSR 2, SPEC 3, TCI 4, Count 5, using the MIT-BIH Arrhythmia Database, Creighton University Ventricular Tachyarrhythmia Database and MIT-BIH Malignant Ventricular Arrhythmia Database. Four quality parameters (e.g., sensitivity, specificity, positive predictivity, and accuracy) were calculated to ascertain the quality of the proposed and other comparing algorithms. Comparative results have been presented on the identification of VTVF, VF and shockable rhythms (VF + VT above 180 bpm). Conclusions The results show significantly improved performance of the proposed EMD-based novel method as compared to other reported techniques in detecting the life threatening cardiac arrhythmias from a set of large databases.

A framework for quantum state-to-state integral and differential cross sections of triatomic reactive scattering using the Multi-Configuration Time-Dependent Hartree (MCTDH) method is introduced, where a modified version of the Heidelberg MCTDH package is applied. Parity of the system is adopted using only non-negative helicity quantum numbers, which reduces the basis set size of the single particle functions in angular degree of freedom almost by half. The initial wave packet is constructed in the space-fixed frame, which can accurately account for the centrifugal potential. By using the reactant-coordinate-based method, the product state-resolved information can be accurately extracted. Test calculations are presented for the H + H2 reactive scattering. This work demonstrates the capability of the MCTDH method for extracting accurate state-to-state integral and differential cross sections. As an efficient scheme for high-dimensional problems, the MCTDH method may be promising for the study of product state-resolved cross sections for polyatomic reactive systems. [ABSTRACT FROM AUTHOR]

We present the time-frame calculated photoabsorption spectrum (ABS), spontaneous Raman excitation profile (REP), femtosecond stimulated Raman spectroscopy (FSRS) spectrum, and femtosecond stimulated Raman excitation profile (FSREP) results of a two-mode and three-mode, three-electronic-states model Hamiltonians containing conical intersections (CIs) along its two upper diabatic electronic states, e1 (dark) and e2 (bright), with and without coupling (nonadiabatic dynamics) along an asymmetric mode. For every electronic state in each model, there is one coupling mode and the rest of the modes are symmetric tuning modes. The CI appears in the Hamiltonian as off-diagonal entries to the potential term that couple the two upper states, in the form of a linear function of the coupling mode. We show that: (a) the ABS, REP, and FSREP for Stokes and anti-Stokes lines contain similar information about the e1 and e2 vibrational bands, (b) the FSRS spectra feature narrow stationary peaks and broader moving peaks contributed by the different resonant components of the third-order polarization terms from perturbation theory, and (c) a relatively strong and narrow stationary band of the allowed first overtone of the asymmetric coupling mode is observed in the Stokes FSREP in the e1 energy region with coupling to e2. [ABSTRACT FROM AUTHOR]

The H/D + HCl/DCl (v0 = 0, j0 = 0) reactions were investigated in the gas phase using the reactant coordinate based time-dependent wave packet method on the BW2 PES [W. Bian and H.-J. Werner, J. Chem. Phys. 112, 220 (2000)]. The total and state-to-state integral and differential cross sections of both the abstraction and the exchange channels were reported over the energy range from threshold to 2.0 eV. The theoretical total exchange integral cross sections agree well with Volpp's experimental measurements but differ from Polanyi's experimental results for H + DCl reaction. The theoretical total abstraction integral cross sections are more than twice as large as the experimental results from the two groups for the H + HCl/DCl reactions. For the four isotope combinations, the total exchange integral cross sections increase monotonically with collisional energy while the abstraction integral cross sections start to decrease at relatively high collision energies. And the abstraction products are predominantly backward and sideways scattered while the exchange products are almost backward scattered. For the two channels, the D + HCl reaction presents the highest reactivity, the H + DCl reaction presents the lowest reactivity, and the H + HCl and D + DCl reactions are in between with the H + HCl reaction having a slightly larger reactivity. [ABSTRACT FROM AUTHOR]

The initial state selected time-dependent wave packet method was employed to calculate the integral cross sections for the H2 + D2 reaction with and without the centrifugal sudden (CS) approximation by including all important K (the projection of the total angular momentum on the body-fixed axis) blocks. With a full-dimensional model, the first fully converged coupled-channel (CC) cross sections for different competitive processes from the ground rotational state were obtained: collision induced dissociation (CID), four-center (4C) reaction and single exchange (SE) reaction. The effect of the total angular momentum J on the reaction dynamics of H2 + D2 and the accuracy of the CS approximation have also been studied. It was found that the CID and SE processes occur in a wide range of J values while the 4C process can only take place in a narrow window of J values. For this reason, the CC cross section for the 4C channel is merely comparable to the SE channel. A comparison of the integral cross sections from CC and CS calculations showed that the CS approximation works well for the CID process but not for the 4C and SE processes, and the discrepancy between the CC and CS cross sections grows larger as the translational energy and/or the vibrational energy increase(s). [ABSTRACT FROM AUTHOR]

The third-order polarization for coherent anti-Stokes Raman scattering (CARS) from a pure state is described by 48 terms in perturbation theory, but only 4 terms satisfy the rotating wave approximation. They are represented by Feynman dual time-line diagrams and four-wave mixing energy level diagrams. In time-resolved (tr) fs and fs/ps CARS from the ground vibrational state, one resonant diagram, which is the typical CARS term, with three field interactions-pump, Stokes, followed by probe-on the ket is dominant. Using the separable, displaced harmonic oscillators approximation, an analytic result is obtained for the four-time correlation function in the CARS third-order polarization. Dlott's phenomenological expression for off-resonance CARS from the ground vibrational state is derived using a three-state model. We calculated the tr fs and fs/ps CARS for toluene and Rhodamine 6G (R6G), initially in the ground vibrational state, to compare with experimental results. The observed vibrational features and major peaks for both tr fs and fs/ps CARS, from off-resonance (for toluene) to resonance (for R6G) pump wavelengths, can be well reproduced by the calculations. The connections between fs/ps CARS, fs stimulated Raman spectroscopy, and impulsive stimulated scattering for toluene and R6G are discussed. [ABSTRACT FROM AUTHOR]

Ultrafast Raman loss spectroscopy (URLS) is equivalent to anti-Stokes femtosecond stimulated Raman spectroscopy (FSRS), using a broadband probe pulse that extends to the blue of the narrow bandwidth Raman pump, and can be described as inverse Raman scattering (IRS). Using the Feynman dual time-line diagram, the third-order polarization for IRS with finite pulses can be written down in terms of a four-time correlation function. An analytic expression is obtained for the latter in the harmonic approximation which facilitates computation. We simulated the URLS of crystal violet (CV) for various resonance Raman pump excitation wavelengths using the IRS polarization expression with finite pulses. The calculated results agreed well with the experimental results of S. Umapathy et al., J. Chem. Phys. 133, 024505 (2010). In the limit of monochromatic Raman pump and probe pulses, we obtain the third-order susceptibility for multi-modes, and for a single mode we recover the well-known expression for the third-order susceptibility, χIRS(3), for IRS. The latter is used to understand the mode dependent phase changes as a function of Raman pump excitation in the URLS of CV. [ABSTRACT FROM AUTHOR]

Collision induced dissociation (CID), four center reaction (4C), and single exchange reaction (SE) in H2 (v1 = high) + D2 (v2 = low) were studied by means of time-dependent wave packet approach within a full-dimensional model. Initial state-selected total reaction probabilities for the three competitive processes have been computed on two realistic global potential energy surfaces of Aguado-Suárez-Paniagua and Boothroyd-Martin-Keogh-Peterson (BMKP) with the total angular momentum J = 0. The role of both vibrationally excited and rotationally excited reagents was examined by varying the initial vibrational and rotational states. The vibrational excitation of the hot diatom gives an enhancement effect on the CID process, while the vibrational excitation of the cold diatom gives an inhibition effect. The rotational excitation of both reagents has a significant effect on the reaction process. The 4C and SE probabilities are at least one order of magnitude smaller than the CID probabilities over the energy range considered. Isotope substitution effects were also studied by substituting the collider D2 by H2 and HD on the BMKP potential energy surfaces. The CID process is most efficient for the H2 + D2 combination and least efficient for the H2 + H2 combination and is different for the 4C and SE processes. [ABSTRACT FROM AUTHOR]

We present a quantum mechanical wave packet treatment of time-resolved femtosecond stimulated Raman spectroscopy (FSRS), or two-dimensional (2D) FSRS, where a vibrational coherence is initiated with an impulsive Raman pump which is subsequently probed by FSRS. It complements the recent classical treatment by Mehlenbacher et al. [J. Chem. Phys. 131, 244512 (2009)]. In this 2D-FSRS, two processes can occur concurrently but with different intensities: a direct fifth-order process taking place on one molecule, and a cascade process comprising two third-order processes on two different molecules. The cascade process comprises a parallel and a sequential cascade. The theory is applied to the 2D-FSRS of CDCl3 where calculations showed that: (a) the cascade process is stronger than the direct fifth-order process by one order of magnitude, (b) the sidebands assigned to C-Cl E and A1 bends, observed on both sides of the Stokes C-D stretch frequency, are not due to anharmonic coupling between the C-D stretch and the C-Cl bends, but are instead due to the coherent anti-Stokes Raman spectroscopy (CARS) and coherent Stokes Raman spectroscopy (CSRS) fields produced in the first step of the cascade process, (c) for each delay time between the femtosecond impulsive pump and FSRS probe pulses, the line shape of the sidebands shows an inversion symmetry about the C-D stretch frequency, and this is due to the 180° phase difference between the CARS and CSRS fields that produced the left and right sidebands, and (d) for each sideband, the line shape changes from positive Lorentzian to dispersive to negative Lorentzian, then to negative dispersive and back to positive Lorentzian with the period of the bending vibration, and it is correlated with the momentum of the wave packet prepared on the ground-state surface by the impulsive pump along the sideband normal coordinate. [ABSTRACT FROM AUTHOR]

The dispersive lines observed in time-resolved femtosecond stimulated Raman spectroscopy (FSRS), using a pair of 809 nm, 3 ps Raman pump, and 840–960 nm ultrashort probe pulse, for the first 500 fs photoisomerization dynamics in the excited state of bacteriorhodopsin, BR* (S1), created by a prior 500 nm, 35 fs actinic pump pulse, have previously been attributed to Raman initiated by nonlinear emission (RINE). We used four-wave mixing energy level diagrams to describe the FSRS process, which include RINE as a subset, and a 29-mode harmonic oscillator model for BR568 in the calculations. Our calculations showed that FSRS of BR* effectively occurs from the ground vibrational state of each of the observed 800–1800 cm-1 modes of S1. The lifetime on S1 determines the linewidth and decay of the dispersive lines, and is estimated to be ∼600 fs, comparable to the stimulated emission decay time. The FSRS dipole couplings are from the ground vibrational state of S1 to high energy vibrational states on BR (S0), and we place a fast decay lifetime of ∼100 fs on S0 which can be attributed to the correlation function from the many unobserved low frequency modes. The FSRS dispersive lines are shown to be due to the inverse Raman scattering term with |0><1| vibrational coherence on the S1 surface, and are not due to RINE with vibrational coherence on the S0 surface. Our calculations show that the RINE process gives rise to broad featureless spectra. [ABSTRACT FROM AUTHOR]

The perturbation theory of stimulated Raman scattering (SRS), with Raman pump on minus pump off and heterodyne detection along the probe direction, is reviewed. It has four third-order polarization terms, labeled as SRS or inverse Raman scattering (IRS): SRS(I), SRS(II), IRS(I), and IRS(II). These four polarizations have a wave packet interpretation. The polarizations, with homogenous and inhomogeneous broadening included, can be written as integrals over four-time correlation functions, and analytic formulas are derived for the latter for multidimensional harmonic potential surfaces with Franck–Condon displacements in the modes which facilitates the calculation of the SRS cross sections. The theory is applied to understand recent experimental results on the femtosecond SRS (FSRS) of a fluorescent dye, rhodamine 6G (R6G), where the Raman pump pulse is about 1 ps long, and the probe pulse is about 10 fs. The calculations compared very well with the R6G experimental results for off-resonance and resonance FSRS spectra spanning both Stokes and anti-Stokes bands, and for negative and positive pump-probe delay times on resonance. [ABSTRACT FROM AUTHOR]

The femtosecond stimulated Raman scattering (FSRS) difference spectra of CDCl3 from the ground potential energy surface, with and without off-resonance impulsive stimulated Raman pumping, taken at various delay times from the impulsive pump by Kukura et al. [Phys. Rev. Lett. 96, 238303 (2006)], showed sidebands of the C–Cl bends with periodic changes in phase as well as having an inversion symmetry to the high and low frequency sides of the Stokes C–D stretch at 2255 cm-1. The semiclassical coupled-wave approach and a one-dimensional (1D) oscillator model for the C–D stretch whose frequency is modulated in time by the C–Cl bends could account for some features of the experimental results. Here, a quantum mechanical investigation is made of the FSRS difference spectra with a modulated 1D oscillator and three-dimensional (3D) harmonic and anharmonic potentials. It is shown that (i) the sidebands are allowed, with or without anharmonic coupling between the C–D stretch and the C–Cl bends, (ii) in the 3D harmonic model the sidebands have mirror symmetry about the Stokes C–D stretch, (iii) in the 3D anharmonic model with appropriate coupling terms between the C–D stretch and the C–Cl bends, the experimental results are well accounted for in both the phase changes in the FSRS difference spectra with time delay as well as the inversion symmetry of the sidebands for the C–Cl bends about the Stokes C–D stretch, (iv) there is a correspondence between the phase changes in the FSRS difference spectra and the wavepacket motion induced by the impulsive pump pulse on the ground potential energy surface as a function of the delay time, and (v) changing the polarization of the impulsive pump pulse, say, directly affects the coordinate dependence of the linear transition dipole moment in the asymmetric mode and hence its phase in the FSRS difference spectra, but not so for the symmetric modes where the displacement of the excited state surface governs the FSRS difference spectra more than the transition dipole moment. This work illustrates the potential of off-resonance FSRS in studying polyatomic molecular dynamics. [ABSTRACT FROM AUTHOR]

We present a complete perturbation theory of stimulated Raman scattering (SRS), which includes the new experimental technique of femtosecond stimulated Raman scattering (FSRS), where a picosecond Raman pump pulse and a femtosecond probe pulse simultaneously act on a stationary or nonstationary vibrational state. It is shown that eight terms in perturbation theory are required to account for SRS, with observation along the probe pulse direction, and they can be grouped into four nonlinear processes which are labeled as stimulated Raman scattering or inverse Raman scattering (IRS): SRS(I), SRS(II), IRS(I), and IRS(II). Previous FSRS theories have used only the SRS(I) process or only the “resonance Raman scattering” term in SRS(I). Each process can be represented by an overlap between a wave packet in the initial electronic state and a wave packet in the excited Raman electronic state. Calculations were performed with Gaussian Raman pump and probe pulses on displaced harmonic potentials to illustrate various features of FSRS, such as high time and frequency resolution; Raman gain for the Stokes line, Raman loss for the anti-Stokes line, and absence of the Rayleigh line in off-resonance FSRS from a stationary or decaying v=0 state; dispersive line shapes in resonance FSRS; and the possibility of observing vibrational wave packet motion with off-resonance FSRS. [ABSTRACT FROM AUTHOR]

Transition state wave packet calculations have been carried out to obtain the thermal rate constants for the H+CH4 reaction on the Jordan-Gilbert potential energy surface. The eight-dimensional model for the X+YCZ3 type of reaction was employed by restricting the nonreacting CZ3 group under a C3V symmetry. We calculated the cumulative reaction probability for the total angular momentum J=0, from which the thermal rate constants were obtained for the temperature range between 250 and 500 K by employing the J-K shifting approximation. It is found that the eight-dimensional rate constants agree very well with the seven dimensional ones, in which the CH bond length in the nonreacting CH3 group is fixed, suggesting that the additional mode for the symmetry stretching in CH3 group does not have any important effect on the reaction within the temperature range considered here. The present transition state wave packet results agree well with rate constants obtained from the previous seven dimensional initial state selected wave packet study, indicating the consistence of the treatments involved in these two studies. On the other hand, it is found that the energy threshold for the cumulative reaction probability for J=0 from the present study is higher than that from the full dimensional multiconfiguration time-dependent Hartree study by about 0.06 eV, resulting in severe discrepancy between the present rate constants and the multiconfiguration time-dependent Hartree results. [ABSTRACT FROM AUTHOR]

The quantum theory for stimulated Raman spectroscopy from a moving wave packet using the third-order density matrix and polarization is derived. The theory applies, in particular, to the new technique of femtosecond broadband stimulated Raman spectroscopy (FSRS). In the general case, a femtosecond actinic pump pulse first prepares a moving wave packet on an excited state surface which is then interrogated with a coupled pair of picosecond Raman pump pulse and a femtosecond Raman probe pulse and the Raman gain in the direction of the probe pulse is measured. It is shown that the third-order polarization in the time domain, whose Fourier transform governs the Raman gain, is given simply by the overlap of a first-order wave packet created by the Raman pump on the upper electronic state with a second-order wave packet on the initial electronic state that is created by the coupling of the Raman pump and probe fields acting on the molecule. Calculations are performed on model potentials to illustrate and interpret the FSRS spectra. [ABSTRACT FROM AUTHOR]

The initial state selected time-dependent wave packet calculations have been carried out to study the title reaction with seven degrees of freedom included by restricting the nonreacting CH3 group under C3V symmetry and the CH bond length in the group. Total reaction probabilities as well as integral cross sections were calculated for the ground and four vibrationally excited reagent states. Our calculation shows that the reactivity is very small for the reaction for collision energy up to 1.0 eV for all the initial states. Initial vibration excitation of CH4, in particular, the CH stretch excitation, enhances the reactivity, but only part of the excitation energy deposited can be used to reduce the reaction threshold. The rate constant for the ground initial state agrees rather well with that from a recent quasiclassical trajectory study and is larger than that from the semirigid vibrating rotor target calculations, in particular, in the low temperature region. On the other hand, the thermal rate constant calculated from the integral cross sections for these five vibrational states is about a factor of 20 smaller than that from the multiconfiguration time-dependent Hartree study. [ABSTRACT FROM AUTHOR]

A time-dependent initial state selected wave packet method has been developed to study the H2(v1=10-11,j1=0)+H2′(v2=0,j2=0)→HH′+HH′ four-center (4C) reaction, and two other competing reactions: the H2+H2′→H+H+H2′ collision induced dissociation (CID) and the H2+H2′→H+HH′+H′ single exchange (SE) reaction, in full six dimensions. Initial state-specific total reaction probabilities for these three competing reactions are presented for total angular momentum J=0 and the effects of reagent vibration on reactions are examined. It is found that (a) the CID process is the dominant process over the whole energy range considered in this study, but the 4C and SE processes also have non-negligible probabilities; (b) the SE process has a lower threshold energy than the 4C process, but the SE probability increases slower than the 4C probability as collision energy increases; (c) the vibrational excitation of H2(v1) is much more efficient than translational motion for promoting these processes, in particular to the CID process. [ABSTRACT FROM AUTHOR]

A new continuous configuration time-dependent self-consistent field method has been developed to study polyatomic dynamical problems by using the discrete variable representation for the reaction system, and applied to a reaction system coupled to a bath. The method is very efficient because the equations involved are as simple as those in the traditional single configuration approach, and can account for the correlations between the reaction system and bath modes rather well. [ABSTRACT FROM AUTHOR]

The effect of the time delay between the picosecond Raman pump and the femtosecond Stokes probe pulse on the Raman gain line shape in femtosecond broadband stimulated Raman spectroscopy (FSRS) is presented. Experimental data are obtained for cyclohexane to investigate the dependence of the FSRS line shape on this time delay. Theoretical simulations of the line shapes as a function of the time delay using the coupled wave theory agree well with experimental data, recovering broad line shapes at positive time delays and narrower bands with small Raman loss side wings at negative time delays. The analysis yields the lower bounds of the vibrational dephasing times of 2.0 ps and 0.65 ps for the 802 and 1027 cm-1 modes for cyclohexane, respectively. The theoretical description and simulation using the coupled wave theory are also consistent with the observed Raman gain intensity profile over time delay, reaching the maximum at a slightly negative time delay (∼-1 ps), and show that the coupled wave theory is a good model for describing FSRS. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Femtosecond broadband stimulated Raman spectroscopy (FSRS) is a new technique that produces high-resolution (time-resolved) vibrational spectra from either the ground or excited electronic states of molecules, free from background fluorescence. FSRS uses simultaneously a narrow bandwidth ∼1–3 ps Raman pump pulse with a continuum ∼30–50 fs Stokes probe pulse to produce sharp Raman gains, at positions corresponding to vibrational transitions in the sample, riding on top of the continuum Stokes probe spectrum. When FSRS is preceded by a femtosecond actinic pump pulse that initiates the photochemistry of interest, time-resolved Raman spectroscopy can be carried out. We present two theoretical approaches to FSRS: one is based on a coupling of Raman pump and probe light waves with the vibrations in the medium, and another is a quantum-mechanical description. The latter approach is used to discuss the conditions of applicability and limitations of the coupled-wave description. Extension of the quantum-mechanical description to the case where the Raman pump beam is on resonance with an excited electronic state, as well as when FSRS is used to probe a nonstationary vibrational wave packet prepared by an actinic pump pulse, is also discussed. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The initial state selected time-dependent wave packet method has been extended to calculate the total reaction probability for atom-triatom reactions with total angular momentum J > 0 by treating both bonds in the triatom reagent reactively. The total exchange and abstraction reaction probabilities for the title reaction with J = 15 calculated with 2 K-blocks (the projection of the total angular momentum on the body-fixed axis) show that one has to treat both OH bonds in the H[SUB2]O reagent reactively for the exchange reaction, but for the abstraction reaction one can treat one OH bond as a spectator bond to get accurate results. This is in accord with what had been found for the total reaction probabilities for J=0 [Phys. Rev. Lett. 89, 103201 (2002)]. The J= 15 reaction probabilities also show that the CS (centrifugal sudden) approximation is inadequate for the title reaction, in particular for the abstraction reaction. The integral cross sections for the abstraction reaction, calculated without the CS approximation but by freezing one OH bond in the H[SUB2]O reagent for the ground and first vibrationally excited states, are found to be substantially larger than the corresponding CS integral cross sections. However, the integral cross section for the ground vibrational state is still much smaller than the existing experimental result. Since the treatment of freezing OH bond is not expected to introduce any noticeable error, it is conceivable that the experiments overestimated the integral cross section for the abstraction reaction. [ABSTRACT FROM AUTHOR]

The initial state selected time-dependent wave packet method has been developed to study the H+ CH[sub 4] reaction in seven dimensions by employing the model developed by Palma and Clary [J. Chem. Phys. 112, 1859 (2000)]. The latter eight-dimensional model only assumes that the nonreacting CH[sub 3] group keeps a C[sub 3V] symmetry in reaction. The CH bond lengths in the nonreacting CH[sub 3] group were fixed in the study to reduce the number of degrees of freedom to seven. Our calculations reveal that it is very important to accurately deal with the umbrella motion of the CH[sub 3] group while studying this reaction. We investigated the effects of the fundamental vibrational excitations of CH[sub 4] on the reaction. Finally, we compare our rate constant for the ground rovibrational initial state with available experimental and other theoretical results. [ABSTRACT FROM AUTHOR]

This paper presents fully converged integral cross sections for the D[sub 2](j[sub 1]=0,2,4)+OH(j[sub 2]=0,2,4)→HOD+D reaction on the YZCL2 potential energy surface. It is found that the influence of reagent rotation excitation on reactivity is relatively mild compared with that of the D[sub 2] vibration excitation, but is fairly important to the thermal rate constant at low temperature. In general, the OH rotation excitation tends to hinder the reaction, and the D[sub 2] rotation excitation tends to enhance the reactivity. The simultaneous reagent rotation has some correlated effect, with the influence of the D[sub 2] rotation excitation considerably dependent on the OH rotation excitation. It is also found that the reaction is strongly dependent on j[sub 12] (the coupled angular momentum between j[sub 1] and j[sub 2]), K[sub 0] (the projection of the reagent rotation on the body fixed axis), and the parity of the system, in particular for either the OH or D[sub 2] rotationally excited initial states, but this dependence becomes relatively weaker as the collision energy increases. Excellent agreement achieved between theory and experiment on the thermal rate coefficients for temperatures up to 400 K clearly shows that the YZCL2 potential energy surface is capable of producing “quantitatively” accurate results for the title reaction. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]