Electronic spectral shifts of aromatic molecule–rare-gas heteroclusters

Shalev, Eli; Ben-Horin, Narda; Even, Uzi; Jortner, Joshua
September 1991
Journal of Chemical Physics;9/1/1991, Vol. 95 Issue 5, p3147
Academic Journal
In this paper, a semiempirical theory for the spectral shifts of the electronic origin of the S0→S1 transition of (aromatic molecule)·(rare-gas)n heteroclusters is advanced and applied. Neglecting the modifications of intermolecular overlap and exchange interactions upon electronic excitation, the dispersive contributions to the spectral shift are evaluated to second order, accounting for finite-size structural features of the large molecule by the utilization of the multicenter monopole representation of the intermolecular interactions. The spectral shifts for nonpolar aromatic hydrocarbons in or on rare-gas heteroclusters are represented in terms of differences between electrostatic interactions involving an electrostatic field (due to the molecular transition monopoles charge distribution) and an induced dipole (originating from the rare-gas polarizability). The transition monopoles incorporated all the one- and two-electron ππ* excitations of the aromatic molecule, which were represented by Hückel or self-consistent molecular orbitals (MO). The dispersive spectral shifts were semiempirically scaled to correct the systematic overestimate of the transition monopoles within these simple MO schemes. The red spectral shift was recast in terms of a sum of two-atom (carbon atom–rare-gas) and three-atom (carbon atom–rare-gas–carbon atom) contributions, which are subsequently summed over the contributions of all the rare-gas atoms, with each term involving products of an electronic factor and a geometric factor. The electronic factors exhibit a linear dependence of the spectral shift on the rare-gas polarizability, while the geometric factors incorporate the structural effects of the contributions of the individual rare-gas atoms to the spectral shift, predicting the nonadditivity of the spectral shift per added rare-gas atom and the exhibition of distinct spectral shifts for different structural isomers. The...


Related Articles

  • Nonadiabatic molecular dynamics simulation of ultrafast pump-probe experiments on I[sub 2] in... Batista, V.S.; Coker, D.F. // Journal of Chemical Physics;5/1/1997, Vol. 106 Issue 17, p6923 

    Focuses on nonadiabatic molecular dynamics simulation of ultrafast pump-probe experiments on solid rare gases. Sample preparation and photoexcitation; Method for calculating pump-probe signals; Diatomics-in-ionic-systems calculation of ion pair states.

  • Rare gas clusters: Solids, liquids, slush, and magic numbers. Beck, Thomas L.; Jellinek, Julius; Berry, R. Stephen // Journal of Chemical Physics;7/1/1987, Vol. 87 Issue 1, p545 

    Simulations by constant energy molecular dynamics have been performed for numerous clusters in the size range N=7–33. Detailed investigations have been conducted on the portions of the caloric curves in which the transition between rigid and nonrigid behavior occurs, to study the N...

  • Sensitivity of liquid-state inherent structure to details of intermolecular forces. Stillinger, Frank H.; LaViolette, Randall A. // Journal of Chemical Physics;12/15/1985, Vol. 83 Issue 12, p6413 

    Temperature dependence of short-range order has been systematically studied in two model atomic liquids, using molecular dynamics computer simulation linked to steepest-descent mapping of configurations onto potential minima. Owing primarily to differing attractive forces, the natural crystal...

  • Trapping of guests in a rare gas matrix: A molecular dynamics simulation. Fraenkel, Ruchama; Haas, Yehuda // Journal of Chemical Physics;3/15/1994, Vol. 100 Issue 6, p4324 

    A molecular dynamics simulation of the trapping of a guest molecule in a rare gas matrix deposition is presented. Using Lennard-Jones pairwise potentials, the shape and size of trapping sites are seen to depend on the preparation conditions, particularly the temperature and the cooling rate. The...

  • Thermal disruption of the inherent structure of simple liquids. LaViolette, Randall A.; Stillinger, Frank H. // Journal of Chemical Physics;11/15/1986, Vol. 85 Issue 10, p6027 

    Short range order in liquids formally may be viewed as an inherent structure (amorphous particle packings) that has been smeared by thermally induced vibrational distortions. In order to study these distortions, we have employed molecular-dynamics computer simulation, with steepest-descent...

  • Structural transitions in metal ion-doped noble gas clusters: Experiments and molecular dynamics.... Prekas, Dimitris; Luder, Christian // Journal of Chemical Physics;3/15/1998, Vol. 108 Issue 11, p4450 

    Investigates the structural transitions of metal ion-doped noble gas clusters using time-of-flight mass spectrometry. Exhibition of magic numbers in the spectra; Correlation of cluster size to icosahedral sequence; Application of molecular dynamics simulations using Lennard-Jones potentials.

  • A dynamic reaction coordinate approach to ab initio reaction pathways: Application to the 1,5 hexadiene Cope rearrangement. Maluendes, S. A.; Dupuis, M. // Journal of Chemical Physics;10/15/1990, Vol. 93 Issue 8, p5902 

    A modified dynamic reaction coordinate algorithm for tracing reaction paths is implemented in the framework of ab initio molecular orbital calculations. This method requires fewer energy and gradient evaluations than the traditional intrinsic reaction coordinate methodology and produces reaction...

  • Molecular dynamics of the A+BC reaction in rare gas solution. Bergsma, John P.; Reimers, Jeffrey R.; Wilson, Kent R.; Hynes, James T. // Journal of Chemical Physics;11/15/1986, Vol. 85 Issue 10, p5625 

    Molecular dynamics are computed for model atom transfers A+BC→AB+C in rare gas solvents at liquid densities. We find that the reaction dynamics can be understood in terms of a simple picture which consists of three stages: (1) activation of reactants, (2) barrier crossing, and (3)...

  • Excited-state dynamics of rare-gas clusters. Scharf, Dafna; Jortner, Joshua; Landman, Uzi // Journal of Chemical Physics;4/1/1988, Vol. 88 Issue 7, p4273 

    In this paper we explore the dynamic implications of energy exchange in electronically vibrationally excited states of mixed rare-gas clusters. The classical molecular dynamics method was applied for the study of vibrational energy flow from electronically excited atomic Xe(3P1) states in...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics