The HeCl2 potential: A combined scattering-spectroscopic study

An empirical intermolecular potential surface is proposed for the He-I 2 ͑B 3 ⌸ u ͒ complex, modeled as a sum of pairwise He-I Morse interactions plus a three-body interaction term. The potential reproduces with very good agreement the spectral blueshifts and vibrational predissociation lifetimes measured for He-I 2 ͑B , Ј͒ in the range Ј= 10-67 of I 2 vibrational excitations. In particular, the accuracy achieved in the description of the experimental data for high Ј levels is attributed to the three-body interaction term included in the potential. The behavior of the potential surface with the I-I separation is analyzed and correlated with the experimental findings.

Section: Introductionmentioning

confidence: 53%

An empirical potential-energy surface for the He–I2(BΠu3) van der Waals complex including three-body effects

Garcı́a-Vela

2005

“…Unfortunately, even the analysis of such sensitive characteristics as the elastic differential scattering cross sections did not yield decisive conclusion so far. 8,36,45 …”

Section: Discussionmentioning

confidence: 99%

First-order intermolecular diatomics-in-molecule potentials. Potential energy surfaces, spectra, and fragmentation dynamics of the Ne⋯Cl2 complex

Buchachenko

Stepanov

1997

Articles you may be interested inA new ab initio intermolecular potential energy surface and predicted rotational spectra of the Ne−H2S complex Microsolvation of the water cation in neon: Infrared spectra and potential energy surface of the H 2 O + -Ne open-shell ionic complex First-order perturbative approximations to the diatomics-in-molecule ͑DIM͒ approach are implemented for studying interactions between the neon atom and chlorine molecule in the X 1 ⌺ g ϩ (0 ϩ ) and B 3 ⌸ u (0 ϩ ) states. Intermolecular DIM perturbation theory ͑IDIM PT1͒ ͓J. Chem. Phys. 104, 9913 ͑1996͔͒, which accounts for the atomic component of spin-orbit interaction, is compared to the anisotropic model by Naumkin and Knowles ͓J. Chem. Phys. 103, 3392 ͑1995͔͒ which is proven to be a first-order approximation to the nonrelativistic DIM approach. An importance of the spin-orbit effects for the ground-state potential energy surface ͑PES͒ is demonstrated. Semiempirical PESs are used in the accurate quantum calculations on the vibrationally averaged geometry, B←X vibronic spectra, and vibrational predissociation dynamics of the Ne•••Cl 2 van der Waals complex. The IDIM PT1 model is shown to provide good agreement with available experimental data. The effects of interaction potential topology on the spectroscopic and dynamic properties of the complex and the relation of DIM-based PESs to the results of ab initio calculations are discussed.

“…If fact, an atom-atom potential has been found to fit quite well a large amount of spectroscopic information. 4,22 It could be said that pairwise model potentials give a reasonable representation for the study of VP in rare gas-halogen molecules. However, more work is needed to determine potential energy surfaces, either using more rigorous semiempirical procedures, such as the diatomic-in-molecule based ones, 23 or through ab initio calculations.…”

Section: Introductionmentioning

confidence: 99%

Vibrational predissociation dynamics of the He79Br2 van der Waals molecule: A quantum mechanical study

González‐Lezana

Hernández

Delgado‐Barrio

et al. 1996

Articles you may be interested in A full-dimensional quantum approach to the vibrational predissociation of tetra-atomic complexes based on the partially-separable time-dependent self-consistent-field approximation Oneatom cage effect in collinear I2(B)-Ar complexes: A timedependent wave packet study Validity of a hybrid quantum/classical approach in photodissociation/recombination of I2 in rare gas matrices A three-dimensional time-dependent self-consistent-field TDSCF approach is proposed to study the vibrational predissociation of the I 2 (B)-Ne van der Waals vdW complex. Jacobian coordinates are used within the assumption of zero-total angular momentum. In the method the total wave function is factorized such that the bending mode of the system is explicitly separated, while the coupling between the remaining two degrees of freedom is treated exactly. The decay dynamics of several resonances corresponding to different initial vibrational states of I 2 is investigated through long-time wave packet propagations. Calculated resonance lifetimes are compared to experimental data and found to be in quantitative agreement with them. The results show that predissociation of the complex is mainly governed by the coupling between the I 2 and the vdW stretching vibrations, whereas the bending mode has a rather weak effect on the dynamics. The good quality of the TDSCF description of this long-time dynamical process is due to the adaptation of the decoupling approximations applied in the method to the physical situation of the system. The validity of the approach is discussed in the light of the results.