Reinvestigation of the HCP electronic spectrum: Experimental determination of D0 for the X state and observation of hyperfine quantum beats in the B state

Mason, Martin A.; Lehmann, Kevin K.
April 1993
Journal of Chemical Physics;4/1/1993, Vol. 98 Issue 7, p5184
Academic Journal
In the laser-induced fluorescence spectrum of HCP, a sharp decrease in fluorescence intensity was observed at 41 680 cm-1. This diminuation in emission intensity is due to a rotationally mediated coupling of the excited vibronic level with the dissociative continuum of the X state; this has allowed us to place an upper limit on D0 for the ground electronic state. A lower limit for D0 can be placed at 41 650 cm-1 since strong emission was observed below this excitation energy. Using the assignments of Johns et al. [Can. J. Phys. 47, 893 (1969)] as a guide, fluorescence decays were recorded from the two B state vibronic bands to determine lifetimes. In addition to determining an unusually long lifetime for both states, the decays were seen to be modulated at four frequencies resulting from the coherent excitation of four nuclear hyperfine levels. This increase in lifetime and magnetic hyperfine interaction arises from a mixing of three singlet and triplet states. The contributing states are tentatively identified.


Related Articles

  • A comparative high-resolution study of predissociation linewidths in the Schumann-Runge bands.... Dooley, P.M.; Lewis, B.R. // Journal of Chemical Physics;9/8/1998, Vol. 109 Issue 10, p3856 

    Presents a comparative study of three advance and complex procedures to evaluate predissociation. Application of vacuum-ultraviolet laser spectroscopy; Laser-induced fluorescence spectroscopy; Vacuum-ultraviolet Fourier-transform spectroscopy; Query on the accuracy of the procedures.

  • Kinetics and thermochemistry of ClCO formation from the Cl+CO association reaction. Nicovich, J. M.; Kreutter, K. D.; Wine, P. H. // Journal of Chemical Physics;3/15/1990, Vol. 92 Issue 6, p3539 

    Laser flash photolysis of Cl2/CO/M mixtures (M=N2, CO, Ar, CO2) has been employed in conjunction with Cl(2PJ) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl(2PJ) +CO↔ClCO as a function of temperature (185–260...

  • Predissociation of the Na[sub 2]3[sup 3]pi[sub g] and other triplet states. Liu, Y.; Li, J. // Journal of Chemical Physics;2/8/1998, Vol. 108 Issue 6, p2269 

    Examines the predissociation of sodium molecule up to the energy of 3s+5p atomic limit. Use of double resonance fluorescence excitation spectroscopy for observing energy levels below 3s+3d limit; Interaction of the 3[sup 3]pi[sub g] state with 3s+3d 2[sup 3]pi[sub g] state; Factors attributing...

  • The binding energies of p-difluorobenzene–Ar,–Kr measured by velocity map imaging: Limitations of dispersed fluorescence in determining binding energies. Bellm, Susan M.; Moulds, Rebecca J.; Lawrance, Warren D. // Journal of Chemical Physics;12/15/2001, Vol. 115 Issue 23, p10709 

    The technique of velocity map imaging has been used to determine the dissociation energies of the van der Waals complexes p-difluorobenzene–Ar and p-difluorobenzene–Kr. The values determined for the S[sub 0], S[sub 1], and D[sub 0] states, respectively, are 337±4, 367±4, and...

  • Direct observation of orbit rotation predissociation in the O2 Schumann–Runge system. Yang, X.; Wodtke, A. M.; Hüwel, L. // Journal of Chemical Physics;2/15/1991, Vol. 94 Issue 4, p2469 

    Laser induced predissociation fluorescence spectroscopy was performed with a tunable Argon fluoride laser in the Schumann–Runge band of O2 in an open atmospheric flame. Simple rotationally resolved spectra of the 10←2 and 11←2 bands were obtained when the fluorescence was...

  • Structure and predissociation of electronically excited HgN2 complex. Yamanouchi, Kaoru; Isogai, Shinji; Tsuchiya, Soji; Duval, Marie-Christine; Jouvet, Christophe; d’Azy, Odile Benoist; Soep, Benoit // Journal of Chemical Physics;9/1/1988, Vol. 89 Issue 5, p2975 

    The structure and the predissociation dynamics of an excited van der Waals (vdW) complex HgN2 which is produced in a supersonic jet, have been investigated by means of laser-induced fluorescence (LIF) spectroscopy. The vibronic systems of the A–X and B–X transitions are analyzed in...

  • Femtosecond fluorescence depletion spectroscopy iof NO[sub 2] multiphoton dissociation dynamics. Lopez-Martens, R.B.; Schmidt, T.W. // Journal of Chemical Physics;10/22/1999, Vol. 111 Issue 16, p7183 

    Studies femtosecond fluorescence depletion spectroscopy of NO[sub 2] multiphoton dissociation dynamics. Photons absorbed by NO[sub 2] before dissociation; Onset of fluorescence depletion at small negative values of tau[sub D].

  • Spectroscopic characterization of the X 1Σ+0 and C 1Π1 states of the ZnKr molecule. Wallace, Ingvar; Ryter, Jarral; Breckenridge, W. H. // Journal of Chemical Physics;1/1/1992, Vol. 96 Issue 1, p136 

    The X 1Σ+0 and C 1Π1 electronic states of the ZnKr van der Waals molecule have been characterized by laser-induced fluorescence spectroscopy. Spectroscopic constants, bond lengths, and dissociation energies are reported for both states. The substantial amount of data now available on...

  • The NaLi 1 1Σ+(X) electronic ground-state dissociation limit. Fellows, C. E. // Journal of Chemical Physics;5/1/1991, Vol. 94 Issue 9, p5855 

    The NaLi 1 1Σ+(X) electronic ground state has been studied by Fourier transform spectroscopy and laser-induced fluorescence up to near the dissociation limit. The fluorescence has been induced by Ar+, Kr+ and dye (DCM and rhodamine 6G) laser lines. Fluorescence spectra have been observed up...


Read the Article


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

Try another library?
Sign out of this library

Other Topics