Analysis of the mass-resolved two-photon spectra of jet-cooled ArKr near Kr*(5p) and Ar*(4s)

Abstract

Articles you may be interested inMassresolved multiphoton ionization spectroscopy of jetcooled Cl2. II. The (2+1) REMPI spectrum between 76 000 and 90000 cm−1 New ͑2ϩ1͒ resonantly enhanced multiphoton ionization ͑REMPI͒ spectra of ArKr in the region of Kr*(5p) and Ar*(4s) between Ϸ92378.8 and 94250.7 cm Ϫ1 are presented. A time-of-flight ͑TOF͒ mass spectrometer was used to obtain single isotopomer data. Four band systems, two previously observed by Dehmer and Pratt ͓J. Chem. Phys. 88, 4139 ͑1988͔͒, and two new ones, have been vibrationally analyzed. Excited state bond lengths have been found from Franck-Condon factor calculations while electronic symmetries were assigned from REMPI spectra recorded with circularly polarized light. Our excited state symmetry assignments differ from those recently proposed by Heck et al. ͓J. Phys. Chem. 99, 17700 ͑1995͔͒. The unusual vibrational band intensity distributions observed for some of the electronic systems are rationalized qualitatively in terms of interstate avoided crossings.

Spectroscopic characterization and potential energy functions of the six low-lying electronic states of ArKr+

“…assumed potential energy functions for the low-lying electronic states of ArKr þ . The analysis of the isotopic shifts determined for the v 0 ¼ 4 level of the intermediate state and of the rotational contour of the vibrational band are fully consistent with the analysis made by Lipson et al [22].…”

“…The 0 Y state of ArKr below the Ar( 1 S 0 ) Y Kr(5p[1/2] 0 ) dissociation limit The transitions from the X 0 þ ground state of ArKr to the first five vibrational levels of the 0 þ state located below the Ar( 1 S 0 ) þ Kr(5p[1/2] 0 ) dissociation limit have been studied by (2þ1) REMPI spectroscopy and assigned by Lipson et al [22]. This excited state of 0 þ symmetry was used as the intermediate state in the (1 þ 1 0 ) two-photon excitation scheme (Equation (1)) to reach the low-lying electronic states of ArKr þ associated with the two Ar( 1 S 0 ) þ Kr þ ( 2 P J , J ¼ 1/2, 3/2) dissociation limits.…”

“…This rotational constant and the measured positions of the band origins from Ref. [22] were further used to determine a Morse potential function (T e þ D e ð1 À e ÀðRÀR 0 Þ Þ 2 ), shown in Figure 1 …”

“…The ground-state potential was taken from [23]. The potential of the intermediate state was obtained by fitting a Morse function to the energy levels presented in [22]. The potential functions of the ionic states are those derived in the present work.…”