Spectroscopy and nuclear dynamics of tetracene–rare-gas heteroclusters

Ben-Horin, Narda; Even, Uzi; Jortner, Joshua; Leutwyler, Samuel
October 1992
Journal of Chemical Physics;10/15/1992, Vol. 97 Issue 8, p5296
Academic Journal
In this paper we report on the electronic spectroscopy of mass-resolved tetracene·Arn (n=1–26) and tetracene·Krn (n=1–14) heteroclusters, utilizing two-photon, two-color near-threshold ionization in conjunction with mass-spectrometric detection. The spectra of the S0 → S1 transition and the ionization threshold of these heteroclusters were monitored. The structured spectral features of the S0 → S1 transition of small- and medium-sized (n=1–8) heteroclusters were attributed to the electronic origins of structural isomers and to their intermolecular vibrations. The S0 → S1 spectra of large (n≥9) heteroclusters are broad and were assigned to inhomogeneous broadening due to the coexistence of isomers, with the spectral feature(s) of each distinct isomer being homogeneously broadened. Isomer-specific inhomogeneous line broadening was interrogated by the observation of isomer-specific ionization potentials for medium-sized (n=6–7) heteroclusters and of the dependence of the relative intensities of the spectral features on the conditions of the supersonic expansion. The ionization thresholds of the tetracene·An (A=Ar,Kr) reveal a linear (or superlinear) n dependence, being qualitatively different from the sublinear n dependence of the spectral shifts. These different patterns of the size dependence can be traced to the different intermolecular interactions which govern excitation and ionization and to the difference in the charge distribution in S0 and in the positive ion. The experimental spectroscopic data for the spectral shifts and the spectral linewidths were simulated in terms of the first and second moments of the classical line shape, which were obtained from Monte Carlo (MC) constant temperature simulations, in conjunction with a two-parameter fit of the excited-state tetracene–rare-gas potential. The Monte Carlo simulations of the structural fluctuation parameters identified...


Related Articles

  • A Uniform Quasi-Classical Description of Radiative Transitions for Asymmetric Rare-Gas Atom—Atom Collisions. Devdariani, A. Z.; Zagrebin, A. L.; Rebentrost, F.; Tserkovnyi, S. I.; Tchesnokov, E. A. // Journal of Experimental & Theoretical Physics;Sep2002, Vol. 95 Issue 3, p413 

    The uniform quasi-classical approximation [14] is used to describe the optical spectra formed during asymmetric collisions between atoms of rare gases in which one of the atoms is in a metastable state. We consider the reactions He(2¹S) + Ne → He(1¹S) + Ne + hω andAr(³P[sub...

  • Spectroscopy of O[sub 3] trapped in rare gas matrices. I. Theoretical model for low-lying... Dahoo, P.R.; Lakhlifi, A.; Chabbi, H. // Journal of Chemical Physics;12/8/1999, Vol. 111 Issue 22, p10192 

    Part I. Examines the spectroscopy of oxygen trapped in rare gas matrices. use of methods in gas phase to calculate the vibrational energies and transition moments for low-lying levels of oxygen; Distortion of the trapping site to minimize the free energy of the molecule-matrix system.

  • Spectroscopy of O[sub 3] trapped in rare gas matrices. II. Vibrational energies and transition... Chabbi, H.; Dahoo, P.R.; Lakhlifi, A. // Journal of Chemical Physics;12/8/1999, Vol. 111 Issue 22, p10202 

    Part II. Discusses the spectroscopy of oxygen trapped in rare gas matrices. Results for molecules trapped in distorted face-centered-cubic and hexagonal-closed-packed lattice structures; Harmonic and anharmonic constants; Symmetry of the potential in which the ozone oxygen nuclei move.

  • Induction of optical transitions through complexation within Hg–rare gas van der Waals systems. Krim, L.; Jouvet, C.; Soep, B.; Onda, K.; Yamanouchi, K.; Visticot, J. P. // Journal of Chemical Physics;10/8/1995, Vol. 103 Issue 14, p5956 

    The high repulsive states of HgAr and HgNe van der Waals complexes, correlating with Hg 6s6d atomic states have been investigated by double resonance spectroscopy, through the first excited state A 30+ and B 31 of the complexes. The repulsive potentials have been fitted through numerical...

  • Simple, sensitive nitrogen analyzer based on pulsed miniplasma source emission spectrometry. Zhe Jin; Yixiang Duan // Review of Scientific Instruments;Dec2003, Vol. 74 Issue 12, p5156 

    The development of pulsed miniplasma source emission spectrometry for trace nitrogen determination in inert gases is described in this article. The instrument consists of a pulsed miniplasma source generated by an in-house fabricated portable high-voltage supply, an optical beam collection...

  • Infrared spectra of diatomic polar molecules in rare-gas liquids. I. Spectral theory. Pérez, J.; Luis, D.; Hernández, A. Calvo; Velasco, S. // Journal of Chemical Physics;9/15/1989, Vol. 91 Issue 6, p3435 

    A theoretical model for the infrared (0–1) band of dilute solutions of diatomic polar molecules in nonpolar rare-gas liquids is presented. The model is based on decomposition of the rotational motion of the diatomic molecule into two limiting cases, according to the Bratos model:...

  • Measurement of stratospheric trace gases by millimeter-wave spectroscopy for an annual cycle at... De Zafra, R.L.; Trimble, C. // Antarctic Journal of the United States;1994, Vol. 29 Issue 5, p253 

    Presents spectroscopic measurements of trace gases in Antarctica's stratosphere. Observations of oxygen trioxide and nitrogen dioxide species; Loss gas phase of HNO3; Emergence of CIOs.

  • Stability of rare gas cluster ions. Hiraoka, Kenzo; Mori, Toshiharu // Journal of Chemical Physics;4/1/1990, Vol. 92 Issue 7, p4408 

    Thermochemical values, ΔH0n-1,n and ΔS0n-1,n, for clustering reactions, Rg+n-1+2Rg=Rg+n+Rg (Rg=He, Ne, Kr, and Xe), were measured with a pulsed electron-beam mass spectrometer. The -ΔH0n-1,n values show a sudden decrease between n=3 and 4, for all rare gases suggesting that the core...

  • Nitrogen content of the mantle inferred from N2-Ar correlation in oceanic basalts. Marty, Bernard // Nature;9/28/1995, Vol. 377 Issue 6547, p326 

    Describes a static mass spectrometry method that allows simultaneous analysis of major volatiles and rare gases. Analysis of gases trapped in vesicles of mid-ocean ridge basalt glasses; Nitrogen-argon ration in the mantle source; Estimation of the nitrogen content of the mantle.


Read the Article


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

Try another library?
Sign out of this library

Other Topics