Interatomic potential for the B³1 state of HgKr related to wing profiles of the Hg 253.7 nm line and to the vibronic spectrum of HgKr molecules

Abstract

The interatomic potential in the excited B31 state of HgKr is established and an estimation of the oscillator strength fXB is given by means of quantum calculations of suitable spectra of HgKr diatomics. Two kinds of experimentally examined spectra are taken into account: a thermally averaged 'hot' absorption spectrum occurring in the far wings of the Hg 253.7 nm line perturbed by Kr and a simple vibronic spectrum arising from B( nu '=0,. . .,14) from X( nu =0) transitions which was observed for supercooled molecules of HgKr. Assuming tentatively that the dipole moment of the transition B from X is independent of interatomic distance, calculations were performed for several forms of relevant potential curves and the resulting spectra were compared with the experimental ones.

Determination of Interatomic Potentials for the X0+, A0+, and B1 States of HgKr from Fluorescence and Excitation Spectra

“…10a along with the results of Okunishi et al (13) and numerical values of Findeisen and Grycuk (8). The analysis carried out in Section 2A(a) indicated that the B state has a Morse-like character and only the long-range tail of its PE curve, very close to the dissociation limit, is dominated by a vdW component.…”

“…The long-range characteristic C 6 , obtained in this procedure, should be compared with those found in the literature: C 6 (6 3 P 1 ) = 1.350 (42) and 0.913 (43), and C 6 (B1) = 1.312 (7,8) and 1.527 (9), all in [cm −1Å 6 ] × 10 6 . Table 1 shows the results for the B1 state together with those determined in earlier investigations.…”

“…The MS potential was applied by Borysow and Grycuk (5), Grycuk and Czerwosz (7), and Findeisen and Grycuk (8) to represent the interatomic potential of the HgKr ground state. In their representations they used three types of MS potential: (n 0 = 11, n 1 = 17) (5), (n 0 = 11, n 1 = 18) (7 ), and (n 0 = 10.63, n 1 = 16.86) (8). None of these, however, would reproduce our experimental fluorescence spectrum, as will be shown below.…”

“…idealibrary.com) and as part of the Ohio State University Molecular Spectroscopy Archives (http://msa.lib.ohio-state.edu/jmsa hp.htm). ergy states (6,8). Initially, Lennard-Jones (LJ) (6)(7)(8)(9)(10)(11)(12) and vdW -C 6 /R 6 functions were used to represent the PE curve of the ground state and the long-range behaviour of the excited state potentials, respectively (6).…”

“…Initially, Lennard-Jones (LJ) (6)(7)(8)(9)(10)(11)(12) and vdW -C 6 /R 6 functions were used to represent the PE curve of the ground state and the long-range behaviour of the excited state potentials, respectively (6). Subsequently, a Maitland-Smith (MS) function joined to a 9.5 reciprocal power function of Powers and Cross (11) and to a vdW component of Ben Lakhdar et al (9) at small and large internuclear separations, respectively, was chosen to represent the X state potential (7,8). However, the repulsive part of this potential was found to have a singularity; as the internuclear separation decreased to zero, the potential decreased to −∞ instead of increasing to +∞.…”