Erratum: Energy distribution in the photodissociation products of van der Waals molecules: Iodine–helium complexes [J. Chem. Phys. <b>71</b>, 1292 (1979)]

An intermolecular potential energy surface for He 2 Br 2 complex in the ground state is calculated at the levels of fourth-order ͑MP4͒ Møller-Plesset and coupled-cluster ͓CCSD͑T͔͒ approximations, using large-core pseudopotential for Br atoms and the aug-cc-pV5Z basis set for He. The surface is characterized by three minima and the minimum energy pathways through them. The global minimum corresponds to a linear He-Br 2 -He configuration, while the two other ones to ''police-nightstick'' and tetrahedral structures. The corresponding well depths are Ϫ90.39/ Ϫ89.18, Ϫ81.23/Ϫ80.78 and Ϫ74.40/Ϫ74.02 cm Ϫ1 , respectively, at MP4/CCSD͑T͒ levels of theory. It is found that results obtained by summing three-body parametrized HeBr 2 interactions and the He-He interaction are in very good accord with the corresponding MP4/CSSD͑T͒ configuration energies of the He 2 Br 2 . Variational calculations using a sum of three-body interactions are presented to study the bound states of the vdW He 2 Br 2 complex. The binding energy D 0 and the corresponding vibrationally averaged structure are determined for different isomers of the cluster and their comparison with the available experimental data is discussed.

Section: Introductionmentioning

confidence: 99%

Ab initio calculations, potential representation and vibrational dynamics of He2Br2 van der Waals complex

Valdés

Prosmiti

Villarreal

et al. 2005

“…[1][2][3][4][5][6] Interest in such species has continued into the present [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] for several reasons. First, the intermolecular forces pertaining to them are relatively simple.…”

Section: Introductionmentioning

confidence: 99%

“…In this way the computer collected a spectrum of mass-selected photoions versus stimulatedRaman frequency. Figure 2 shows intermolecular ILSRS spectra measured for the perprotonated and perdeuterated benzene- 4 He complexes. In addition to the rotational-Raman features peaked near 4 cm Ϫ1 , one sees broad structure for both species centered near 16.5 cm Ϫ1 .…”

mentioning

confidence: 99%

Computational and experimental investigation of intermolecular states and forces in the benzene–helium van der Waals complex

Lee

Chung

Felker

et al. 2003

A study of the intermolecular potential-energy surface ͑IPS͒ and the intermolecular states of the perprotonated and perdeuterated benzene-He complex is reported. From a fit to ab initio data computed within the coupled cluster singles and doubles including connected triples model for 280 interaction geometries, an analytic IPS including two-to four-body atom-atom terms is obtained. This IPS, and two other Lennard-Jones atom-atom surfaces from the literature, are each employed in dynamically exact ͑within the rigid-monomer approximation͒ calculations of Jϭ0 intermolecular states of the isotopomers. Rotational constants and Raman-scattering coefficients for intermolecular vibrational transitions are also calculated for each of the three surfaces. The calculated results are compared with experimental results reported herein pertaining to intermolecular Raman spectra of benzene-He. The calculated rotational constants are compared with experimental values from the literature. The fitted IPS of this work leads to calculated observables that match the experimental results very well. The IPSs from the literature are not as successful, specifically in regard to the intermolecular Raman spectra.

“…Here, we extrapolate these results and in a first step, we express the global PESs for the Ne 2 Br 2 complex in the form (1). It is important to note that, even if this proves to be a good approximation for Rg = He and Ne due to the weakness of the vdW bonds, neglecting 4-body contributions in the global PES of clusters containing heavier Rg atoms could eventually fail.…”

Section: B Potential Energy Surfacesmentioning

confidence: 99%

Quasi-classical trajectories study of Ne2Br2(B) vibrational predissociation: Kinetics and product distributions

Arbelo-González

González-Martínez

Reed

et al. 2012

The vibrational predissociation of the Ne 2 Br 2 (B ) van der Waals complex has been investigated using the quasi-classical trajectory method (QCT), in the range of vibrational levels v ′ = 16-23. Extensive comparison is made with the most recent experimental observations [Pio et al., J. Chem. Phys. 133, 014305 (2010)], molecular dynamics with quantum transitions (MDQT) simulations [Miguel et al., Faraday Discuss. 118, 257 (2001)], and preliminary results from 24-dimensional Cartesian coupled coherent state (CCCS) calculations. A sequential mechanism is found to accurately describe the theoretical dynamical evolution of intermediate and final product populations, and both QCT and CCCS provide very good estimates for the dissociation lifetimes. The capabilities of QCT in the description of the fragmentation kinetics is analyzed in detail by using reduced-dimensionality models of the complexes and concepts from phase-space transport theory. The problem of fast decoupling of the different coherent states in CCCS simulations, resulting from the high dimensionality of phase space, is tackled using a re-expansion scheme. QCT ro-vibrational product state distributions are reported. Due to the weakness of the vdW couplings and the low density of vibrational states, QCT predicts a larger than observed propensity for ∆v ′ = −1 and −2 channels for the respective dissociation of the first and second Ne atoms.