Nadine Halberstadt

Three‐dimensional quantum mechanical study of Ne⋅⋅⋅Cl2 vibrational predissociation

Three‐dimensional quantum mechanical calculations for vibrational predissociation of the Ne⋅⋅⋅Cl2 van der Waals complex are presented and compared with experiments. Lifetimes and final rotational state distributions were obtained for the two processes: (i) Ne⋅⋅⋅Cl2(X,v=1) →Ne+Cl2(X,v=0) and (ii) Ne⋅⋅⋅Cl2(B,v=11) →Ne +Cl2(B,v=10,9) where v denotes the vibrational quantum number of Cl2 and X and B specify electronic states of Ne⋅⋅⋅Cl2 which correlate with the X 1∑+0g and B 3∏+0u states of the free Cl2 molecule, respectively. The van der Waals interaction potential was taken to have the same form in the X and B states. At short distances, it is described by a sum of Morse pairwise potentials between the Ne atom and each of the Cl atoms, and between the neon atom and the center of mass of Cl2. At large distances the potential switches to an anisotropic van der Waals interaction with R−6 and R−8 dependence. The parameters were adjusted so that the T‐shaped configuration the potential matched the one determined...

Photofragmentation of the Ne⋯ICl complex: A three-dimensional quantum mechanical study

Converged three‐dimensional quantum mechanical calculations for photofragmentation of the Ne⋅⋅ICl van der Waals molecule in the energy region of the electronically excited B(3∏0+) state of ICl are presented and compared with experiments. Lifetimes and final state distributions for the ICl fragments were determined for vibrational predissociation from the lowest van der Waals level in the B(v’=2) channel. Good agreement between theory and experiment was achieved using a sum of atom–atom pairwise potentials. This potential energy surface predicts the equilibrium geometry of the complex to be bent at 140° with the Ne atom towards the Cl end of ICl. The diabatic vibrational golden rule (DVGR) approximation, as well as the rotational infinite order sudden approximation (RIOSA), have been tested again the full 3D calculations. Analysis of the quasibound wave function reveals that the highly inverted rotational distribution of the ICl fragments observed in the experiment, is not due to zero‐point bending motion....

Theory of mode specific vibrational predissociation: The HF dimer

Quantum mechanical close coupling calculations on (HF)2 vibrational predissociation are presented. The model considers vibrational excitation of the proton donor monomer. The other momomer is frozen at its equilibrium position. The linewidth (lifetime) and final state rotational distribution of the initially vibrationally excited HF were calculated using the artificial channel method. The potential surface was taken from Cournoyer and Jorgensen. The calculated linewidth is in good agreement with recent experimental measurements. This result is drastically different from what is obtained in the collinear model, merely reflecting the important influence of the rotational–vibrational coupling in the highly anisotropic systems. The final rotational distribution of the initially excited HF monomer is highly inverted. The possibility of a rotational in conjunction with a conventional vibrational HF laser is raised.

Capture and ionization of argon within liquid helium droplets

Liquid helium droplets of initial mean cluster size, 〈N〉, ranging from 600 to 8000 atoms are doped with argon using the pick-up technique. The doped clusters are ionized by electron impact, and the resulting fragment ions are monitored as a function of argon pressure in the pick-up volume. Analysis of the pressure dependent ion signals is used to determine (1) the probability for charge transfer from He+ to the Ar atoms within the droplet, and (2) the probability for fragmentation of the Ark subclusters upon ionization. The measured charge transfer probability from He+ to Ar ranges from 0.05±0.02 for clusters of mean original size 〈N〉=8000 to 0.26±0.05 for 〈N〉=600. Charge transfer to the Ark constituent results in the following qualitative trends; a single Ar atom yields HenAr+ ions; Ar2 mainly yields Ar2+, and Ar3 mainly fragments to yield Ar2+. Simulations of the results are performed to extract information on how the charge transfer and fragmentation processes within the ionized droplet dependent on th...

Quantum dynamical calculations for the vibrational predissociation of the He-ICl complex: Product rotational distribution

Three‐dimensional quantum close‐coupling calculations are presented for the vibrational predissociation of He–ICl B state complexes containing two quanta of ICl vibrational excitation. The dynamics are evaluated for the lowest quasibound van der Waals levels of He–ICl with total angular momentum J=0 and 1. The vibrational predissociation lifetime and final ICl B(v=1, j ) rotational distribution are calculated using the golden rule approximation. The calculated ICl product rotational distributions are broadly bimodal with maxima at j=7 and 15, as experimentally observed. The computed rotational distributions exhibit pronounced oscillations, which are expected to be suppressed when averaged over the initial angular momentum distribution sampled in the experiment. The theoretical analysis points to the dominant role of final‐state interactions in determining the rotational distribution of the ICl fragments. The zero‐point bending motion of the He–ICl complex and the coupling between the initial and final vib...

Theoretical investigation of the temperature dependence of the O+O2 exchange reaction

The exchange reaction 16O+18O2→16O18O+18O and, in particular, its dependence on the transition state region is investigated by classical trajectories on three potential energy surfaces, all based on high-level electronic structure calculations. The first one is the original potential recently constructed by Siebert, Schinke, and Bittererova [Phys. Chem. Chem. Phys. 3, 1795 (2001)]; it has a very small barrier above the O+O2 asymptote. The second potential is a modification of the first one in that the transition state region is adjusted according to new electronic structure calculations on higher levels of theory; it has a small barrier below the asymptote. The third potential is obtained by artificially removing this barrier. The variation of the exchange reaction cross section with collision energy and the magnitude of the thermal rate constant at and below room temperature depend drastically on the shape of the potential at intermediate distances. The second potential, which is believed to represent th...

The HeCl2 potential: Atom–atom and ab initio compared to experiment

Two forms for the HeCl2 potential are compared to the available experimental data. First, an atom–atom form that incorporates the recently measured anisotropic He–Cl potential is used. The anisotropy of this potential is slight, and its strengths and weaknesses are similar to previous potentials in which the He–Cl interaction was treated as isotropic. In particular, the fit to the scattering data is poor. Second, a fit to ab initio points calculated using Mo/ller–Plesset perturbation theory to fourth order was performed. The resulting potential is much more anisotropic than any potential previously proposed and tested for HeCl2. This potential fits the rotationally resolved excitation spectra as well as do previous empirical potentials, and is consistent with certain features of the total differential scattering data with which previous potentials were not. Although the ab initio potential has a global minimum in the linear configuration, the probability distribution of the ground vibrational level still ...

Vibrational predissociation of the Ar⋅⋅⋅Cl2 van der Waals complex: The small molecule limit for intramolecular vibrational redistribution

A converged three‐dimensional quantum treatment of vibrational predissociation in the Ar⋅⋅⋅Cl2(B3Π0u+,υ′) van der Waals complex is presented. The potential energy surface used is a sum of pairwise Morse atom–atom interactions adjusted asymptotically to a C6/R6+C8/R8 anisotropic van der Waals form. Calculations have been performed in the energy region of Ar⋅⋅⋅Cl2(B,υ’=6, 10, and 11) excited levels. In agreement with the experimental findings, the final rotational distribution of Cl2 is found to be strongly dependent on the initial υ’ state being excited, as well as on the number of vibrational quanta lost in the vibrational predissociation process. The role of intramolecular vibrational redistribution for υ’=10 and 11 for which the Δυ=−1 channel is closed is also studied. It is found that the vibrational predissociation (VP) dynamics are dominated by the coupling of the zero‐order ‘‘bright’’ state with a single ‘‘dark’’ state from the υ’−1 manifold of van der Waals vibrationally excited states which then d...

High resolution spectroscopy of the He79Br2 van der Waals molecule: An experimental and theoretical study

The structure, dissociation dynamics, and intermolecular potential energy surfaces of the He79Br2 van der Waals molecule have been studied using high resolution, two color, pump–probe laser induced fluorescence spectroscopy and three dimensional quantum mechanical calculations. A conical nozzle produces higher centerline cluster densities than a standard nozzle, and allows data collection further downstream from the nozzle. This yields improved signal to noise ratios and lower Doppler widths. He79Br2 is found to have a T‐shaped average geometry with He to Br2 center‐of‐mass distances of 3.98 A and 4.11 A for the X and B states, respectively, somewhat longer than previously reported. Spectra were also obtained for excitation to excited bending levels of the van der Waals coordinate. However, these spectra have yet to be rotationally assigned. Vibrational predissociation line widths for the B state of He79Br2 have been measured for three new vibrational levels and range from 0.036 cm−1 for B, v′=8 to 0.062 ...

A theoretical study of the Ar2HCl van der Waals cluster

A theoretical method for treating the dynamics of polymeric van der Waals clusters is developed, based on an adiabatic separation of the heavy atom motions. The method is applied to the calculation of spectroscopic parameters for the complex Ar2HCl, and the results are compared with experimental data from high‐resolution microwave studies. Potentials based on pairwise additivity and the known Ar–HCl pair potential are used. Small discrepancies between experiment and theory are observed, and it seems likely that these are attributable to the effects of three‐body forces rather than to deficiencies of the pair potentials used. High‐resolution spectroscopy of van der Waals clusters shows great promise as a tool for investigating nonadditive intermolecular forces.