Rydberg states of NO trapped in rare gas matrices

Abstract

Several new progressions consisting of broadbands have been observed in the absorption spectra of NO trapped in rare gas matrices. They are identified as the blue shifted transitions to the n=3 (A 2Σ+,C 2Π,D 2Σ+) and n=4 (E 2Σ+,K 2Π,M 2Σ+) Rydberg states of NO in Ne matrices and to the n=3 Rydberg states in Ar, Kr, and Xe matrices. Linewidths (50 to 180 meV) and matrix shifts (0.3 to 1.2 eV) decrease from neon to xenon matrices. For each matrix, the shifts decrease according to the symmetry of the excited state orbital, in the sequence sσ–pσ–pπ. An attempt to apply the quantum defect formula with values, for the Rydberg constant and the ionization potential of the matrix isolated molecule taken from literature, fails to describe the vertical transition energies of n=3 and n=4 states in neon matrices. On the other hand, using the adiabatic energies of 3sσ and 4sσ states to generate a series shows that the vertical transitions of n≥5 states lie in the ionization continuum. This could explain the nonobservation of n>4 states in Ne matrices. In the heavier matrices, this model predicts n=4 states but their existence is not borne out by experiment. The Wannier model also fails to describe these transitions.

Rydberg and charge transfer states of F atoms in neon matrices

“…The sum P ϩ ϩV 0 is about 0.75 eV and is similar to NO/Ne. 40 This means-in the sign convention used here-that the energy V 0 , which is required to inject a free electron into solid neon is 0.75 eV larger than the energy gained by the lattice polarization from the positive core. Estimates of P ϩ lie in the range of 1-1.8 eV ͑Ref.…”

“…Excitation and emission spectra of the free neon excitons show a larger barrier to the formation of Ne 2 * than to the formation of Ne*, though the former is lower in energy. 40,46 The charge transfer excimer can be viewed as a limit of separation in the exciton state, and the barriers to the formation of the Ne ϩ and Ne 2 ϩ will follow those of Ne* and Ne 2 *.…”

Direct Observation of Microscopic Solvation at the Surface of Clusters by Ultrafast Photoelectron Imaging

“…33 Isolation in a solid rare gas matrix represents a case of extreme density, manifested by the largest blue shifts and broadening. 29 Here, the matrix data show a number of features, some identical to the gas phase spectrum, others not: (a) band 1 (shoulder) at ∼340 nm in the gas phase spectrum is very weakly distinguished in Ne matrices, but it becomes gradually more conspicuous in Ar and Kr matrices, although less clear-cut than in the gas phase. In the latter two matrices, it appears clearly blue shifted with respect to the gas phase.…”

An ab initio study of Xe–NO(X2II) and Xe–NO(A2Σ+) potential energy surfaces

“…On the other hand, the present pool of experimental data is still insufficient for the complete characterization of many phenomena occurring on the atomic scale. The latter is the case for photoinduced processes consisting of cage relaxation upon Rydberg excitation of impurities in rare gas (RG) solids [23][24][25][26][27][28][29][30], such as (NO, Hg, I 2 )-doped RG solids [24,25,29,31] and H 2 solids [24,27,30,32,33].…”