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We apply the so-called variational Gaussian wavepacket approximation (VGA) for conducting both real- and imaginary-time dynamics to calculate thermal correlation functions. By considering strongly anharmonic systems, such as a quartic potential and a double-well potential at high and low temperatures, it is shown that this method is partially able to account for tunneling. This is contrary to other popular many-body methods, such as ring polymer molecular dynamics and the classical Wigner method, which fail in this respect. It is a historical peculiarity that no one has considered the VGA method for representing both the Boltzmann operator and the real-time propagation. This method should be well suited for molecular systems containing many atoms. [ABSTRACT FROM AUTHOR]

In scattering theory, the Wigner–Smith time delay, calculated through a phaseshift derivative or its multichannel generalization, has been demonstrated to measure the amount of delay or advance experienced by colliding particles during their interaction with the scattering potential. Fetic, Becker, and Milosevic argue that this concept cannot be extended to include photoionization, viewed as a half-scattering experiment. Their argument is based on the lack of information about scattering phaseshifts in the part of the wavefunction (satisfying the ingoing-wave boundary condition) going to the detector. This article aims to test this claim by examining a photodetachment process in a simple 1D model with a short-range symmetrical potential. Using time-dependent perturbation theory with a dipole interaction, the relevant wavepacket of the outgoing particle is analyzed and compared to the free wavepacket as a reference. Our findings confirm that, indeed, a time delay arises in the liberated fragmentation wavepacket, which is expressed as an energy derivative of the scattering phaseshift. Our study highlights that the source of the phaseshift content in the wavepacket arriving at the detector is the dipole matrix element, which is a direct consequence of imposing the ingoing-wave boundary condition. We illustrate our results through numerical simulations of both the non-free and free wavepackets. The amount of the observed time delay is found to be half of that appearing in a typical scattering experiment. [ABSTRACT FROM AUTHOR]

In this work, we describe a toolbox to realize and probe synthetic axial gauge fields in engineered Weyl semimetals. These synthetic electromagnetic fields, which are sensitive to the chirality associated with Weyl nodes, emerge due to spatially and temporally dependent shifts of the corresponding Weyl momenta. First, we introduce two realistic models, inspired by recent cold-atom developments, which are particularly suitable for the exploration of these synthetic axial gauge fields. Second, we describe how to realize and measure the effects of such axial fields through center-ofmass observables, based on semiclassical equations of motion and exact numerical simulations. In particular, we suggest realistic protocols to reveal an axial Hall response due to the axial electric field E5, as well as axial cyclotron orbits and chiral pseudo-magnetic effect due to the axial magnetic field B5.

A unidirectional, weakly dispersive nonlinear model is proposed to describe the supercritical bifurcation arising from hydroelastic waves in deep water. This model equation, including quadratic, cubic, and quartic nonlinearities, is an extension of the famous Whitham equation. The coefficients of the nonlinear terms are chosen to match with the key properties of the full Euler equations, precisely, the associated cubic nonlinear Schrödinger equation and the amplitude of the solitary wave at the bifurcation point. It is shown that the supercritical bifurcation, rich with Stokes, solitary, generalized solitary, and dark solitary waves in the vicinity of the phase speed minimum, is a universal bifurcation mechanism. The newly developed model can capture the essential features near the bifurcation point and easily be generalized to other nonlinear wave problems in hydrodynamics.

A multitude of ultrafast photoinduced reactions in organic semiconductors are governed by the close interplay between nuclear and electronic degrees of freedom. From biological light-harvesting and photoprotection to organic solar cells, the critical electronic dynamics are often precisely synchronized with and driven by nuclear motions, in a breakdown of the Born-Oppenheimer approximation. Ultrafast time-domain Raman methods exploit impulsive excitation to generate nuclear wavepackets and track their coherent evolution through these reaction pathways in real time. This tool of vibrational coherence has recently been applied to study singlet fission, a carrier multiplication process with the potential to boost solar cell efficiencies which has been under intense mechanistic investigation for the past decade. In this review, we present the essential features of the spectroscopic techniques and discuss how they have been used to elaborate a new perspective on the singlet fission mechanism. It is now established that ultrafast triplet-pair formation is driven by vibronic coupling, whether fission is exothermic or endothermic, and thus that full understanding of singlet fission requires explicit consideration of nuclear dynamics. Despite broad qualitative agreement between different vibrational coherence methods, differences in the detailed observations and interpretation raise important questions and pose new challenges for future research.

Single photons and entangled photons lie at the heart of photonic quantum technologies, whose optimal performances are normally reached when the purity of the single or entangled photons is high. However, the multiphoton emission, dissipation, and decoherence in practical realizations always lead to the degradation of the single‐ and entangled‐ photon quality. The purification of single or entangled photons is thus valuable to restore the quantum states and enhance the performance of quantum technologies. The applications of wavepacket shaping, an emerging quantum optics tool to manipulate the single‐ and entangled‐ photon wavefunctions, to purify single and entangled photons are reviewed. In particular, by modulating the single photons emitted from optically excited room‐temperature quantum dots, it is shown that the fast‐decaying multiphoton emission can be eliminated to obtain a low value of g(2)(0) that is independent of the excitation power. It is also shown that the two‐photon interference and polarization entanglement of the non‐degenerate biphotons from spontaneous parametric down‐conversion can be restored after modulating the biphotons with a periodic function. The works have potential applications in long‐distance quantum communication and linear optical quantum computation. [ABSTRACT FROM AUTHOR]

Photodissociation of HOBr is an important step in the reaction network of the depletion of ozone in stratosphere. Here, we report the first three-dimensional potential energy surfaces for the lowest three singlet states for HOBr, based on high level multi reference configuration interaction calculations. Quantum dynamics calculations are performed with a real wavepacket method, yielding not only absorption spectra but also internal state and angular distributions of the photodissociation fragments. Our results agree quantitatively with the measured total absorption cross sections of HOBr in the ultraviolet region and reproduce well the observed vibrationally cold and rotationally hot OH/OD fragments via photodissociation of HOBr/DOBr at 266 nm. In addition, we predict that the recoil anisotropy parameters for OH/OD are close to the limiting value of a parallel transition, suggesting a rapid dissociation process at 266 nm following an in-plane transition from the ground state (11A′) to the 21A′ state. This is consistent with the experimental conclusion derived from the measured rotational alignment. However, spin and electronic angular momenta need to be taken into account in the future to achieve a more quantitative agreement with experiment. Our work is expected to motivate further experimental investigations for this benchmark system. [ABSTRACT FROM AUTHOR]

We present the non-adiabatic, conical-intersection quantum dynamics of the title collision where reactants and products are in the ground electronic states. Initial-state-resolved reaction probabilities, total integral cross sections, and rate constants of two H2 vibrational states, v0 = 0 and 1, in the ground rotational state (j0 = 0) are obtained at collision energies Ecoll ≤ 3 eV. We employ the lowest two excited diabatic electronic states of HeH2+ and their electronic coupling, a coupled-channel time-dependent real wavepacket method, and a flux analysis. Both probabilities and cross sections present a few groups of resonances at low Ecoll, whose amplitudes decrease with the energy, due to an ion-induced dipole interaction in the entrance channel. At higher Ecoll, reaction probabilities and cross sections increase monotonically up to 3 eV, remaining however quite small. When H2 is in the v0 = 1 state, the reactivity increases by ~2 orders of magnitude at the lowest energies and by ~1 order at the highest ones. Initial-state resolved rate constants at room temperature are equal to 1.74 × 10−14 and to 1.98 × 10−12 cm3s−1 at v0 = 0 and 1, respectively. Test calculations for H2 at j0 = 1 show that the probabilities can be enhanced by a factor of ~1/3, that is ortho-H2 seems ~4 times more reactive than para-H2.

This paper presents an analytic solution for the aerodynamic noise generated by a traveling wavepacket passing near the edge of a rigid semi-infinite flat plate. The solution is derived in the time domain for a wavepacket of either constant or spatially-varying wavenumber, for which novel closed-form expressions are obtained for the incident and scattered sound fields. The case of a varying wavepacket constitutes a surrogate model for turbulent flow distortions caused by the edge region and its geometry. This modeling approach permits a relaxation of the frozen gust assumption that is commonly used in the analytical prediction of trailing-edge noise, whereby the local vorticity is assumed to be unaffected by the edge. Our results shed light on the role that spatial variations of the vortical field near the trailing edge have on the incident and scattered sound contributions to the acoustic far field. In particular, we find that the wavenumber modification has a significant effect on the incident field but not on the scattered field amplitude. However, the phase difference between the incident and scattered fields depends strongly on the spatial variation in the wavepacket wavenumber, which leads to a variation in the sound level and directivity of the total pressure field. • Wavenumber modification used to study effect of relaxing the frozen gust assumption. • Novel closed-form expressions derived for the far field acoustic pressure. • Scattered field amplitude is not affected by wavenumber modification near the edge. • Wavenumber modification affects the incident field amplitude and phase difference. [ABSTRACT FROM AUTHOR]

Development of efficient numerical methods for quantum reactive scattering process by using time-dependent quantum wavepacket method is always necessary in the field of quantum chemistry, due to the complexity of the system, and the large computational efforts required. To perform quantum reactive scattering calculation in hyperspherical coordinates, as the hyper-radial (ρ) increases, the potential well along the angular degree of the freedom (χ) becomes narrower and narrower, which thus requires denser and denser grid points for well describing the diatomic vibrational motion. This makes the time dependent wavepacket packet calculations prohibitively difficult using hyperspherical coordinate when the reaction involves long range interaction potential or requires long absorption potential. In this study, we developed a stair-shaped grid based quantum wavepacket method to overcome this difficulty. In this method, the hyper-radial is partitioned into multidomains in the form of a stair-shape. In each domain, different grid point numbers could be applied for the angular degree of the freedom (χ). In this way, the computational effort could be saved. For numerical example, the stair-shaped grid based quantum wavepacket method is applied to compute the total reaction probability of the F+HCl (v 0 , j 0) → HF+Cl reaction , which involves long range interaction potential. The results are compared with those calculated with the reactant coordinate-based (RCB) Jacobi coordinate and Interaction Asymptotic Region Decomposition (IARD) method. [Display omitted] • This study introduces a novel stair-shaped grid-based quantum wavepacket method for efficient quantum reactive scattering calculations. • The method addresses computational challenges in hyperspherical coordinates with increasing hyper-radial, demanding denser grid points. Especially for reactive systems with long-range interaction potential. • By partitioning the hyper-radial into stair-shaped domains with variable grid points in kinematics angle, the method optimizes computational resources. • The approach is applied to calculate the total reaction probability for the F+HCl (v 0 , j 0) → HF+Cl reaction, featuring a long-range interaction potential. • Comparative analysis with established methods, such as reactant coordinate-based method and the Interaction Asymptotic Region Decomposition method, underscores the accuracy and efficiency of the proposed stair-shaped grid-based quantum wavepacket method. [ABSTRACT FROM AUTHOR]

Spatial instability waves associated with low-frequency noise radiation at shallow polar angles in the chevron jet are investigated and are compared to the round counterpart. The Reynolds-averaged Navier-Stokes equations are solved to obtain the mean flow fields, which serve as the baseflow for linear stability analysis. The chevron jet has more complicated instability waves than the round jet, where three types of instability modes are identified in the vicinity of the nozzle, corresponding to radial shear, azimuthal shear, and their integrated effect of the baseflow, respectively. The most unstable frequency of all chevron modes and round modes in both jets decrease as the axial location moves downstream. Besides, the azimuthal shear effect related modes are more unstable than radial shear effect related modes at low frequencies. Compared to a round jet, a chevron jet reduces the growth rate of the most unstable modes at downstream locations. Moreover, linearized Euler equations are employed to obtain the beam pattern of pressure generated by spatially evolving instability waves at a dominant low frequency St=0.3, and the acoustic efficiencies of these linear wavepackets are evaluated for both jets. It is found that the acoustic efficiency of linear wavepacket is able to be reduced greatly in the chevron jet, compared to the round jet. [ABSTRACT FROM AUTHOR]

This study is motivated by the need for physical models for the jet noise source to be used in practical noise prediction schemes for propulsion–airframe integration concepts. The basis for the source model is an amplitude-modulated traveling wave—the wavepacket. The source is parameterized and the parameters are determined by minimizing the difference between the modeled and experimental sound intensity distributions in the far field. Even though the pressure signal that reaches the far field is highly filtered, sufficient information is available to construct a wavepacket with reasonable physical characteristics. A simple stochastic extension of this concept shows a connection between the shape of the far-field sound pressure level spectrum and the emission polar angle. It suggests that the broadening of the spectrum with increasing polar angle from the downstream axis can be explained on the basis of a single noise source (the wavepacket), rather than the prevailing model of two distinct noise sources, one coherent and the other incoherent. [ABSTRACT FROM AUTHOR]

In general, the aerosols mixed in air medium can be regularly manipulated by means of the interactions between the aerosols and the acoustic field. The manipulable properties of aerosols can be engineered through geometric parameter and acoustic resonance condition of the underlying device. The aerosols manipulated by modulated multiple acoustic wavepackets (MAWP) in acoustic resonance condition is proposed and demonstrated in this paper, whose application belongs to an efficient aerosol removal technique. The experimental results indicated that the removal efficiency of aerosols was mainly influenced by the different harmonic order. The technique and process proposed in this paper was feasible for industrial application. The MAWP is modulated by means of the synthetic standing wave field at the resonant frequency 1.268 kHz. The aerosol manipulation processes through MAWP consist of the aerosol shift, collision aggregation and deposition between the dot and the anti-neck of a single wavepacket. As a visual inspection confirming standing wave, the processes may also be applied in modulating the MAWP simultaneously. The manipulation efficiency can be increased due to the increase of wavepacket amount under the same operating conditions. The acoustic radiation force causes shift and accumulation of aerosol in waveguide and the secondary radiation force enhances collision aggregation and deposition thereof. The initial number concentration of particles < 2.5 μm (resp. larger than 2.5 μm) was about 517,488 1/cf 3 (resp. 51,918 1/cf 3 ). Under the action of these forces, the aerosols in waveguide were aggregated and deposited onto the inner wall of waveguide. At the end of experiment, the final number concentration of particles < 2.5 μm (resp. larger than 2.5 μm) is about 59,096 1/cf 3 (resp. 392 1/cf 3 ). The PM 2.5 content of aerosols used in experiment is about 91%. The removal coefficients are larger than 85%. The deposition stripe distribution shows the specific pattern associated with a wavepacket. The surface of the stripe particles is covered with the uniform small hollows (~ 105.7–177.7 nm), and plenty of nanoscale particles (~ 13.66–16.55 nm) are grown around the surface of small hollows. It may be possible to develop a new way for large scale and batch aerosol processing to apply to the prospective emission control of industrial aerosols. [ABSTRACT FROM AUTHOR]

We used a reflected shock tube to investigate the acoustic signature of a hot jet at the far-field. Experiments were performed at Mach = 1.4 and a total temperature of T = 950 Kelvin. Far-field acoustic signatures of the hot jet at six polar angles θ = 15˚ to θ = 90˚ from the jet axis) were measured and imaged by the means of continuous wavelet transform in scalograms. The results were compared with experiments from a steady test facility at similar test conditions. Further, the primary characteristics of noise events in jet far-field were compared with analytical models considering wavepacket as the main source of jet noise. The results indicate that higher frequency events at θ = 90˚ occur with a small time shift relative to the low azimuthal mode base event. This phenomenon might be the main reason why the acoustic signal at the side angles behaves more noisily than at low polar angles. [ABSTRACT FROM AUTHOR]

We consider wavepackets composed of two modulated carrier Bloch waves with opposite group velocities in the one dimensional periodic Nonlinear Schrödinger/Gross–Pitaevskii equation. These can be approximated by first order coupled mode equations (CMEs) for the two slowly varying envelopes. Under a suitably selected periodic perturbation of the periodic structure the CMEs possess a spectral gap of the corresponding spatial operator and allow families of exponentially localized solitary waves parametrized by velocity. This leads to a family of approximate solitary waves in the periodic nonlinear Schrödinger equation. Besides a formal derivation of the CMEs a rigorous justification of the approximation and an error estimate in the supremum norm are provided. Several numerical tests corroborate the analysis. [ABSTRACT FROM AUTHOR]

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A large eddy simulation (LES) is performed for two subsonic jets with a Reynolds number of $$Re=10^5$$ , which have different core temperatures, i.e., the cold and hot jet. The far-field overall sound pressure levels (OASPL) and noise spectra are well validated against previous experimental results. It is found that the OASPL is raised by heating at shallow angles. The most energetic coherent structures are extracted with specified frequencies using the filter based on the frequency domain variant of the snapshot method of proper orthogonal decomposition (POD). The $$m=0,1$$ modes have high coherence of near-field pressure for both jets, while the coherence of $$m=0$$ modes is enhanced greatly by heating. Based on the coherent structures, spatial wavepackets are educed and the characteristics of growth, saturation and decay are analyzed and compared between the two jets in detail. The results show that heating would enhance the linear growth rate for high frequency components, and nonlinear growth rates for low frequency components in general, which are responsible for higher OASPL in the hot jet. The far-field sound generated by wavepackets is computed using the Kirchhoff extrapolation, which matches well with that of LES at shallow angles. This indicates that the wavepackets associated with coherent structures are dominant sound sources in forced transitional turbulent jets. Additionally, the present POD method is proven to be a robust tool to extract the salient features of the wavepackets in turbulent flows. [ABSTRACT FROM AUTHOR]

We illustrate the state of the art in time-dependent calculations on systems of chemical interest. In particular, our exposition covers the Gaussian multiconfiguration time-dependent Hartree/variational multiconfiguration Gaussian approach in nuclear dynamics, where the scope is that of explaining dynamical effects in various physicochemical processes. Conversely, the Rice-Ramsperger-Kassel-Marcus/master equation kinetic methods are also examined, used to calculate rate constants of gas phase processes (used in the modeling of combustion, atmospheric, and astrochemical processes). [ABSTRACT FROM AUTHOR]

This work explores the vibrational state-selective photoassociation (PA) in the ground state of the HX (X = F, Cl, I) molecule by solving the time-dependent Schrödinger equation. For the three systems, the vibrational level of is set to be the target state and the PA probability of the target state is calculated and compared by considering different initial collision momentums. It is found that the PA probabilities are in accordance with Franck-Condon overlap integral for the HI and HCl systems, but it is not the case for the HF system. Moreover, for the HF system, it is shown that the PA probability of the target state is largest and the multiphoton transition is more likely to occur. This work compared the photoassociation dynamics of the HX (X = F, Cl, and I) systems by using the time-dependent wave packet method. The PA probabilities are in accordance with Frank-Condon overlap integral for the HI and HCl systems, but it is not the case for the HF system. Moreover, for the HF system, it is shown that the PA probability of the target state is largest and the multiphoton transition is more likely to occur. [ABSTRACT FROM AUTHOR]

Abstract: The time-dependent wave packet quantum method under centrifugal sudden (CS) approximation has been employed to investigate the dynamics of the exchange reaction H+OH+ based on an accurate potential energy surface [Martínez et al., J. Chem. Phys. 120 (2004) 4705]. The reaction probability dependence with collision energy, the weighed partial wave contributions to the integral cross sections, and the integral cross sections of the exchange reaction H+OH+ in the collision energy range of 0.0–1.0eV with reactant OH+ in the rotational state j i =0 and vibrational states v i =0–4 are calculated. The calculated time evolution of CS probability density distribution in logarithmic scales at total angular momentum J =0 clearly indicates that the convex structure in the reaction path of the exchange H+OH+ reaction has significant influence on the dynamics of title reaction. [Copyright &y& Elsevier]

A multiconfiguration time-dependent Hartree method oriented toward calculations of a non-Born-Oppenheimer nature has been applied to the calculation of the dynamical properties of a confined H atom. The calculation is fully six-dimensional and does not take into account constraints arising from linear or angular momentum conservation. The orbital evolution is monitored and the energy level spectrum of the system, as well as the dependence of the results on the decomposition of the Hamiltonian and on the correlation between radial degrees of freedom, is determined. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

The nonlinear evolution of a finite-amplitude disturbance in a 3-D supersonic boundary layer over a cone was investigated recently by Liu et al. using direct numerical simulation (DNS). It was found that certain small-scale 3-D disturbances amplified rapidly. These disturbances exhibit the characteristics of second modes, and the most amplified components have a well-defined spanwise wavelength, indicating a clear selectivity of the amplification. In the case of a cone, the three-dimensionality of the base flow and the disturbances themselves may be responsible for the rapid amplification. In order to ascertain which of these two effects are essential, in this study we carried out DNS of the nonlinear evolution of a spanwise localized disturbance (wavepacket) in a flat-plate boundary layer. A similar amplification of small-scale disturbances was observed, suggesting that the direct reason for the rapid amplification is the three-dimensionality of the disturbances rather than the three-dimensional nature of the base flow, even though the latter does alter the spanwise distribution of the disturbance. The rapid growth of 3-D waves may be attributed to the secondary instability mechanism. Further simulations were performed for a wavepacket of first modes in a supersonic boundary layer and of Tollmien-Schlichting (T-S) waves in an incompressible boundary layer. The results show that the amplifying components are in the band centered at zero spanwise wavenumber rather than at a finite spanwise wavenumber. It is therefore concluded that the rapid growth of 3-D disturbances in a band centered at a preferred large spanwise wavenumber is the main characteristic of nonlinear evolution of second mode disturbances in supersonic boundary layers. [ABSTRACT FROM AUTHOR]

Using the three-state model and time-dependent wavepacket method, the influence of the parameters of the intense femtosecond laser field on the wavepacket dynamic process of the double-minimum potential state 51Σ+and the population of the ground and diabatic electronic states of NaLi are investigated. The calculations show that different femtosecond laser parameters result in different influences on the evolution of the wavepacket and the population of NaLi. With increasing laser intensity and wavelength the diabatic coupling strength betweenAandBstates first strengthens and then weakens. The population interchanges betweenAandBstates when the laser pulse disappears. The above results provide the suggestions and useful information for one to achieve quantum manipulation of the molecule in an experiment. [ABSTRACT FROM AUTHOR]

We show here for a simple model system that the wavepacket dynamics in the interaction region can be described by a superposition of the non-Hermitian exponential divergent eigenfunctions of the physical Hamiltonian. We demonstrate how it is possible to obtain the complex eigenvalues and also the corresponding resonance eigenfunctions from the propagation of the wavepacket within the framework of the standard formalism of quantum mechanics. The general results demonstrated here for a simple model can lead to two different types of computational applications: (i) for systems where one can obtain the resonance energies and lifetimes as well as their corresponding eigenfunctions it is possible to study the evolution of the physical properties solely based on the initially populated resonance states without the need to propagate the wavepacket; (ii) for molecular systems where it is quite difficult to solve the non-Hermitian time-independent Schrödinger equation and obtain molecular resonance energies and functions. For this type of problem, the methods presented here enable one to evaluate the topology of complex potential energy surfaces from the wavepacket propagation and facilitate the study of the nuclear dynamics of ionizing molecular systems. [ABSTRACT FROM AUTHOR]

Magnetic interaction was included in the simulation of the evolution of the electron wave-packet of the hydrogen molecular ion H2+ in femtosecond intense pulsed laser fields applied along the molecular axis. This evolution was followed by solving 2-D time-dependent Schrödinger equation at some fixed inter-nuclear separations. Magnetic interaction effects at non-relativistic intensities induced a phase shift in the time evolution of the electron wave-packet, and an excess z-component angular momentum as compared with the results obtained in the absence of magnetic interaction. Furthermore, the H2+ electron WP displacement showed a drift and wiggling in the propagation direction which was different from that observed under pure electric field of the laser pulse. The local fluxes at different points of the 2-D space borders and the time-dependent induced angular momentum are calculated and analyzed. [ABSTRACT FROM AUTHOR]

Abstract: Discussion on wavelength dependent “anharmonic” effects in a pump–probe signal for a system of wavepacket on one- and two-dimensional harmonic potentials was given. The Fourier power spectrum of the signal, calculated for a model composed of a three-state electronic system coupled to a set of displaced harmonic oscillators, depends on the pulse duration. Condition under which the wavepacket motion in the harmonic potential substantially deviates from that of the classical point mass is derived. The Fourier power spectrum has enhanced components with frequencies of harmonics even in a system composed of ideally harmonic potentials. Utility of the Fourier analysis of the spectrum for clarification of the squeezed molecular vibrational state is discussed. Calculated oscillatory behavior in phase of a pump–probe signal, as a function of probe frequency, was discussed in terms of a two-dimensional effect on a pump–probe signal. [Copyright &y& Elsevier]

Abstract: The photoinduced dynamics of pyrrole at the – and – conical intersections has been investigated by multi-mode time-dependent quantum wave-packet calculations. Diabatic potential-energy surfaces have been constructed for both conical intersection using accurate multi-reference ab initio electronic-structure calculations. In addition to the NH stretching coordinate, the three (four) symmetry-allowed coupling modes of () symmetry have been considered for the – (–) conical intersections. Wave-packet dynamics calculations have been performed for three-dimensional models, taking account of the two dominant coupling modes of each conical intersection. The electronic population-transfer processes at the conical intersections, the branching ratio for the dissociation to the ground and excited states of the pyrrolyl radical, and their dependence on the initial preparation of the system have been investigated. It is shown that the excitation of the NH stretching mode strongly enhances the photodissociation rate, while the excitation of the strongest coupling mode has a pronounced effect on the branching ratio of the photodissociation process. Although the inclusion of the second (weaker) coupling mode has little effect on the electronic population dynamics, it leads to interesting changes of the nodal pattern of the wave packet at the conical intersections. The calculations provide insight into the effect of the multiple coupling modes on the process of direct photodissociation through a conical intersection. [Copyright &y& Elsevier]

We present a Gaussian wavepacket approach for curve-crossing dynamics that only requires a single Gaussian wavepacket per surface. Unlike other Gaussian wavepacket approaches to curve-crossing dynamics, the present method does not rely upon probability density being built up on a non-adiabatically coupled surface by the break-up of an evolving wavepacket. Thus, our trial solution for the time-dependent Schrodinger equation comprised of a single Gaussian wavepacket per non-adiabatically coupled surface. We also present a generalization of the method to treat multi-dimensional systems that is based on the time-dependent Hartree approximation. We present numerical results for both single and multi-dimensional curve-crossing dynamics and compare them to the exact results. [ABSTRACT FROM AUTHOR]

Abstract: Electronic structure (CASPT2) calculations have been performed for the lowest 2Π and 4Σ− states of the NCO system. To create the potential energy surfaces, the generalized discrete variable representation (GDVR) method has been used. Wave packet calculations have been performed for the collinear O+CN reaction on both surfaces. These are the first reported quantum dynamics calculations on this reaction. State-to-state reaction probabilities are presented. On the 2Π surface, which has an almost 6eV deep well, we obtain structure in the reaction probabilities at low kinetic energies but at higher energies they are smooth. The 4Σ− surface is highly exoergic and vibrationally non-adiabatic dynamics is observed. The 4Σ− surface has an early barrier and as a result we find that translational energy more efficiently promotes the reaction than vibrational energy does. The wave packet results are compared with QCT results. Generally the agreement is good as would be expected but some notable differences are found, particularly for reaction out of the vibrational ground state. [Copyright &y& Elsevier]

Molecular vibration of several modes in blue-phase polydiacetylene-3-butoxycarbonylmethylurethane (PDA-3BCMU) was real-time observed by 5-fs pump-probe measurement. The contribution of the vibrational wavepackets in the ground state and in the excited state in the signal were separated by multichannel measurements The C=C stretching mode in the ground state starts to oscillate p-out-of-phase with the C=C stretching mode. The structure of PDA-3BCMU in the geometrically relaxed state is not pure butatriene-type but more like acetylene-type. The frequencies of C=C and C=C stretching modes there were determined by singular value decomposition method to be 1472 ± 6 cm -1 and 2092 ± 6 cm -1 , respectively. The double and triple bond stretching frequencies in the ground state which are 1463 ± 6 cm -1 and 2083 ± 6 cm -1 , respectively. [ABSTRACT FROM AUTHOR]

The present paper shows the failure of CS (centrifugal sudden or coupled states) approximation in the time-dependent (TD) quantum wave packet calculation for the exoergicity reaction O + NH on the 1A′ potential energy surface [Guadagnini, Schatz and Walch, J Chem Phys102:774 (1995)] that has double deep wells. In order to show this, total reaction probabilities and rate constants for the title reaction are presented in this study with the CS approximation and the CC (close-coupling) method, respectively. The results show that by carrying out the wave packet propagation to several picoseconds with the CC method, we can resolve all the resonance features for the title reaction and the differences between the CS and the CC become larger as J becomes larger. When J becomes larger the agreement between the CS and the CC gets progressively worse. The failure of the CS approximation can be explained with the results of double deep wells, which cause long propagation time and make the coupling of K states important. [ABSTRACT FROM AUTHOR]

Plates are common structural elements of most engineering structures, including aerospace, automotive, and civil engineering structures. The study of plates from theoretical perspective as well as experimental viewpoint is fundamental to understanding of the behavior of such structures. The dynamic characteristics of plates, such as natural vibrations, transient responses for the external forces and so on, are especially of importance in actual environments. In this paper, we consider natural vibrations of an elastic plate and the propagation of a wavepacket on it. We derive the two-dimensional equations that govern the spatial and temporal evolution of the amplitude of a wavepacket and discuss its features. We especially consider wavenumber-based nearly bichromatic waves and direction-based nearly bichromatic waves on an elastic plate. The former waves are defined by the waves that almost concentrate the energy in two wavenumbers, which are very closely approached each other. The latter waves are defined by the waves that almost concentrate the energy in two propagation directions and two propagation directions are very close each other. The fact that the solution of the governing equation for wavenumber-based nearly bichromatic waves is stable is also shown. [ABSTRACT FROM AUTHOR]

Abstract: In this contribution, recent advances in the theory of laser and, to a lesser extent, of scanning tunneling microscope (STM) induced cleavage of bonds between an adsorbate and a solid surface, will be reviewed. Special emphasis will be given to the quantum dynamics of electronically non-adiabatic reactions. [Copyright &y& Elsevier]

The primary act of charge separation was studied in P+BA– and P+HA– states (P, primary electron donor; BA and HA, primary and secondary electron acceptor) of native reaction centers (RCs) of Rhodobacter sphaeroides R-26 using femtosecond absorption spectroscopy at low (90 K) and room temperature. Coherent oscillations were studied in the kinetics of the stimulated emission band of P* (935 nm), of absorption band of BA– (1020 nm) and of absorption band of HA (760 nm). It was found that in native RCs kept in heavy water (D2O) buffer the isotopic decreasing of basic oscillation frequency 32 cm –1 and its overtones takes place by the same factor ∼1.3 in the 935, 1020, and 760 nm bands in comparison with the samples in ordinary water H2O. This suggests that the femtosecond oscillations in RC kinetics with 32 cm –1 frequency may be caused by rotation of hydrogen-containing groups, in particular the water molecule which may be placed between primary electron donor PB and primary electron acceptor BA. This rotation may appear also as high harmonics up to sixth in the stimulated emission of P*. The rotation of the water molecule may modulate electron transfer from P* to BA. The results allow for tracing of the possible pathway of electron transfer from P* to BA along a chain consisting of polar atoms according to the Brookhaven Protein Data Bank (1PRC): Mg(PB)-N-C-N(His M200)-HOH-O = BA. We assume that the role of 32-cm –1 modulation in electron transfer along this chain consists of a fixation of electron density at BA– during a reversible electron transfer, when populations of P* and P+BA– states are approximately equal. [ABSTRACT FROM AUTHOR]