Electronic transitions in collinear H+ + D2 (ν = 0) → HD+ (ν = 0,1) + D via classical trajectories in complex time and complex phase space

A semiclassical treatment of electronic transitions in the collinear rearrangement H⁺ + D₂ (ν = 0) → HD⁺ (ν = 0,1) + D is presented. The treatment represents an extension of Stueckelberg's method for a single nuclear degree of freedom to collisions involving several nuclear degrees of freedom. The classical limit of scattering amplitudes (S-matrix elements) is calculated for the transition between the two adiabatic potential energy surfaces corresponding to the two lowest singlet states of HD⁺₂. S-matrix elements are constructed from trajectories propagating in complex time and complex phase space, which make localized transitions between the two surfaces by crossing their complex line of intersection. The action along each trajectory acquires an imaginary part, which contributes exponential damping to the corresponding amplitude for electronic transition.     

Radiative decay of nonstationary system

When a finite quantum system, say a fluorescent molecule is attached to a bulk surface and excited by a short laser pulse, the decay dynamics of the system is modulated by the surface and the signal is enhanced due to the bulk surface. We have considered the decay dynamics of a model of displaced distorted molecule whose excited potential surface is coupled to a continuum and then this first continuum is in turn coupled to a second continuum. In the short time scale there is a coherent exchange of energy between the system molecule and the first continuum states. In the long time scale the energy of the whole system plus first continuum drains out to the final continuum states. A dendrimer nanocomposite with the gold surface shows an enhanced light emission. This can be qualitatively understood from the model we proposed here. We have numerically studied the various potential parameters of the molecule which can affect the signal. When the potential surfaces are flat, the band structure of the first continuum states along with its initial excitation has some nontrivial effect on the profile of the radiative decay.     

Radiative neutralization of small clusters impinging on solid surfaces

Light emission during the interaction of slow singly-charged clusters with solid surfaces is studied theoretically. More precisely, we consider positive ions of Ag _n clusters (n = 1...5) impinging on silver surfaces. In such systems, the charge transfer process involved during the cluster-surface interaction is mainly resonant capture. However, photon emission due to radiative capture is also a possible charge transfer channel. Our simple theoretical model including both processes allows us to calculate the light spectra and the total photon yield for the different cluster sizes, n. Our results show that light emission strongly depends on the electronic level dynamics of the clusters in front of the surface, providing a tool for electronic structure analysis of atoms, clusters and solid surfaces.     

Theoretical studies of the potential energy surface and wavepacket dynamics of the Li3 system

The three-dimensional (3D) potential energy surface of the ground state of Li₃ was determined by the multireference configuration interaction method. The vibrational motions and pseudorotation were investigated by a 3D time-dependent wavepacket formalism. The analytical expression of the 3D surface is given and the results of vibrational analyses at several critical points are presented. The low-lying excited states of Li₃ were examined for the C _{2 v} structure and the vertical and adiabatic excitation energies were calculated. The ground and singlet excited states of Li₂ were calculated and their spectroscopic constants compare well with the experimental values. A 3D wavepacket calculation was performed for simulations of the stimulated emission pumping spectrum in which the A state was taken as an intermediate. The recurrences of the autocorrelation functions were characterized by classical trajectory calculations. The autocorrelation functions obtained by wavepacket propagation are reproduced well by the accumulation of the classical trajectories in the short-time region. Received: 2 July 1998 / Accepted: 3 September 1998 / Published online: 8 February 1999     

Effects of surface passivation on the exciton dynamics of CdSe nanocrystals as observed by ultrafast fluorescence upconversion spectroscopy

The exciton dynamics of CdSe nanocrystals are intimately linked to the surface morphology. Photo-oxidation of the selenium surfaces of the nanocrystal leads to an increase in radiative decay efficiency from both the band edge and deep trap emission states. The addition of the primary amine hexadecylamine curtails nonradiative excitonic decay attributed to the dangling surface selenium orbitals by passivation of those trap sites by the methylene protons on the amine, leading to enhanced band edge emission and the absence of deep trap emission. Furthermore, CdSeZnSe core/shell nanocrystals are not immune from contributions from surface states because of the alignment of the band structures of the core and shell materials.     

Dynamic correlations with time-dependent quantum Monte Carlo

In this paper, we solve quantum many-body problem by propagating ensembles of trajectories and guiding waves in physical space. We introduce the "effective potential" correction within the recently proposed time-dependent quantum Monte Carlo methodology to incorporate the nonlocal quantum correlation effects between the electrons. The associated correlation length is calculated by adaptive kernel density estimation over the walker distribution. The general formalism is developed and tested on one-dimensional helium atom in laser field of different intensities and carrier frequencies. Good agreement with exact results for the atomic ionization is obtained.     

Carbon clusters in a storage ring

Anions of fullerenes and small carbon clusters C _n ^- have been stored in the storage ring ASTRID and observed decays on a millisecond time scale are interpreted as electron emission from metastable excited states. For the fullerenes, the fast decay is caused by thermionic emission, quenched by radiative cooling. The observed decay times are longest for the magic numbers n = 50, 60, reflecting a reduction of the thermal radiation due to the electronic shell structure. This statistical interpretation is supported by experiments on thermionic emission from C ₆₀ ^- molecules heated by a Nd:YAG laser pulse. For anions of small carbon clusters (n = 2 - 9) there is a metastable component for n = 2 and for odd n but no metastability on a millisecond time scale for even n. The excited states are suggested to be quartet states decaying by Auger emission.     

Classical S matrix: Application of the Bessel uniform approximation to a chemical reaction

The Bessel uniform approximation developed by Stine and Marcus is applied to the collinear H + H₂ reaction on Diestler's potential energy surface no. 3 to which we have previously applied other orders of approximation of classical S matrix theory. It appears that an accurate treatment of this system by classical S matrix theory requires interference of real and complex trajectories. Calculations were also performed on two other potential energy surfaces in order to more clearly understand the interrelationships of previous semiclassical and quasiclassical studies of this reaction.     

Dynamics of collisions of hydroxyl radicals with fluorinated self-assembled monolayers

We present a classical trajectory study of the dynamics of collisions between OH radicals and fluorinated self-assembled monolayers (F-SAMs). The gas/surface interaction potential required in the simulations has been derived from high-level ab initio calculations (focal-point-CCSD(T)/aug-cc-pVQZ) of various approaches of OH to a model fluorinated alkane. The two lowest-energy doublet potential energy surfaces considered in the electronic structure calculations have been averaged to produce a pairwise analytic potential. This analytic potential has been subsequently employed to propagate classical trajectories of collisions between OH and F-SAMs at initial conditions relevant to recent experiments on related systems. The calculated rotational distributions of the inelastically scattered OH agree well with the experiment, which serves to validate the accuracy of the simulations. Investigation of the dynamics of energy transfer for different initial rotational states of OH indicates that an increase in the initial rotation of OH results in increases in both the final average OH rotational and translational energy and in a slight decrease in the amount of energy transferred to the surface. Analysis of the dynamics as a function of the desorption angle of OH from the surface shows that while there is a correlation between the final scattering angle and OH’s amount of final translational energy, the amount of rotational energy in OH is largely independent of the desorption angle. The mechanism of the collisions is found to be mostly direct; in about 90% of most trajectories, OH only collides with the surface once before desorbing, which exemplifies the rigidity of fluorinated monolayer surfaces and their inability to efficiently accommodate gas species.     

Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations where other criteria, such as the energy gap criterion or the extent of population transfer, fail. We further propose to estimate this quantum fidelity efficiently with a generalization of the dephasing representation to multiple surfaces. Two variants of the multiple-surface dephasing representation (MSDR) are introduced, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics (LMFD). The LMFD can be interpreted as the Ehrenfest dynamics of an ensemble of nuclear trajectories, and has been used previously in the nonadiabatic semiclassical initial value representation. In addition to propagating an ensemble of classical trajectories, the MSDR requires evaluating nonadiabatic couplings and solving the Schro?dinger (or more generally, the quantum Liouville-von Neumann) equation for a single discrete degree of freedom. The MSDR can be also used in the diabatic basis to measure the importance of the diabatic couplings. The method is tested on three model problems introduced by Tully and on a two-surface model of dissociation of NaI.     

Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9H-carbazole-Based ortho-Carboranyl Luminophores

The photophysical properties of closo-ortho-carboranyl-based donor–acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of 1F and 4T were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π–π* transition of the 9-phenyl-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λ_em = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S₁) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for 1F < ‒H for 2P < ‒CH₃ for 3M < ‒C(CH₃)₃ for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.     

Excitation of analytes and enhancement of emission intensities in a d.c. plasma jet: a critical review leading to proposed mechanistic models

Experimental data and theoretical criteria are used to critically review existing models for analyte emission enhancement in the 3-electrode d.c. plasma (DCP). The analytical zone is characterized as a non-optically thin recombining plasma in partial thermodynamic equilibrium (PTE). Spectrochemical excitation the authors ascribe largely to: (1) argon resonance line radiative transport; (2) inversion of optically pumped argon states; (3) inversion of analyte populations by Franck-Condon collisions with argon; (4) energy cascading in analytes via a multitude of channels. Adding an easily ionized element (EIE): (1) induces additional resonance line radiative transfer; (2) raises electron densities in cooler, analyte-rich plasma margins; (3) locally increases argon optical absorption cross sections via Stark broadening; (4) redistributes ohmic heating. Coupling between the proposed mechanisms is non-linear. Relationships between radiative transfer and collisional redistribution and (1) background suppression by EIE and (2) analyte emission enhancement by helium are also examined. Similarities between DCP and inductively coupled plasma (ICP) excitation mechanisms are noted and practical implications are addressed.     

A quasiclassical trajectory study of vibrational energy transfer in collisions involving intermolecular attraction of moderate strength

Monte Carlo selected, quasiclassical trajectories have been computed on six potential energy hypersurfaces possessing potential minima or “wells” up to 50 kJ mol^?1 deep. The aim of the investigation has been to examine how vibrational energy transfer in A + BC(υ = 1) collisions is promoted by intermolecular attraction of moderate strength. Here results are reported for the mass combination m_A = 20 u, m_B = 1 u, m_C = u. The results show that even quite slight intermolecular attraction can enhance energy transfer, as long as the attraction does not just depend on the separation of A from the center-of-mass of BC. The mean loss of vibrational energy does not depend only the well depth but also on its “location” (in particular, the difference in r_BC at the minimum and in isolated BC) and on the angular anisotropy of the potential. Large transfers of energy do not occur only in complex-forming collisions; indeed, a high fraction of trajectories on all surfaces are direct but show similar transfer of energy as in the more complex trajectories on the same surface. The results of the calculations are discussed in relation to the mechanisms and rates of vibrational relaxation in collisions between radicals and between species. such as HF + HF, capable of forming hydrogen bonds.     

Rydberg series of autoionizing states in strong laser fields

We study the behavior of Rydberg series of resonances excited by intense laser fields. Our approach is based on a semiclassical formalism for the evolution in time of the atomic states coupled by the laser. The atomic system is described by a two-channel model in a Multichannel Quantum Defect Theory approach. We calculate the total ionization and the photoelectron spectrum after a certain interaction time. We present results both for on-resonance and off-resonance excitation of the series. We employ a more or less realistic pulse shape that corresponds to a narrow Fourier bandwidth. We show that the effects of the non-resonant members of the series on the photoelectron spectra can be important and we study it both as a function of laser intensity and as a function of the interaction time. We also show that our model correctly describes the Rabi oscillations between the ground state and the excitedAI state when the field is sufficiently strong.     

Lifetime of the He2(e), He2(d) and He2(f) states

Starting from the He₂(a) state absorption and induced fluorescence experiments were performed using a narrow band dye laser. The saturation intensity for the He₂(e)←He₂(a) transition yields a radiative lifetime of τ=(67±10) ns. Time resolved measurements of the laser induced fluorescence yield the radiative lifetimes for the states He₂(e): (57±10) ns, He₂(d): (25±5) ns and He₂(f): (19±5) ns. From the time integrated fluorescence data the collisional quenching rates between the above states were determined.     

Optical emission spectroscopy and modeling of plasma produced by laser ablation of titanium oxides

In the present study, the time evolution of electron number density, of electron, atom and ion temperatures, of plasma produced by KrF excimer laser ablation of titanium dioxide and monoxide targets, are investigated by temporally and spatially resolved optical emission spectroscopy over a wide range of laser fluence from 1.7 to 6 J cm⁻², oxygen pressures of 10⁻²–10⁻¹ torr and in a vacuum. A state-to-state collisional radiative model is proposed for the first time to interpret the experimental results at a distance of 0.6 mm from the target surface, in vacuum and for a time delay from 100 to 300 ns from the beginning of the laser pulse. In particular, we concentrate our attention on problems concerning the existence of the local thermodynamic conditions in the laser-induced plasma and deviation from them, as observed in our experiment. The numerical model proposed for calculating the electron number density and the population densities of atoms and ions in excited states give good quantitative agreement with the experimental results of the optical emission spectroscopy measurements.     

Natural radiative lifetimes in the 5snd 1 D 2 series of SrI

Natural radiative lifetimes have been measured for the 5snd ¹ D ₂ series in SrI for the previously not measuredn=10, 11 and 12 states. The measurements connect earlier measurements in lower and higher states in this heavily perturbed series. The lifetimes were determined using pulsed laser excitation and time-resolved detection.     

Angle-dependent resonance of localized and propagating surface plasmons in microhole arrays for enhanced biosensing

The presence of microhole arrays in thin Au films is suited for the excitation of localized and propagating surface plasmon (SP) modes. Conditions can be established to excite a resonance between the localized and propagating SP modes, which further enhanced the local electromagnetic (EM) field. The co-excitation of localized and propagating SP modes depends on the angle of incidence (θ _exc) and refractive index of the solution interrogated. As a consequence of the enhanced EM field, enhanced sensitivity and an improved response for binding events by about a factor of 3 to 5 was observed with SPR sensors in the Kretschmann configuration for a set of experimental conditions (λ _SPR, θ _exc, and η). Thus, microhole arrays can improve sensing applications of SPR based on classical prism-based instrumentation and are suited for SP-coupled spectroscopic techniques.