Excitation Spectroscopy of Krypton Molecular Rydberg States

An excitation spectrum of the Kr(,2) ('3)(SIGMA)(,u)('+)(1(,u),O(,u)('-)) excimer has been obtained for 335 (LESSTHEQ) (lamda) (LESSTHEQ) 445 nm and 480 (LESSTHEQ) (lamda) (LESSTHEQ) 545 nm, and Rydberg series of krypton dimers have been observed. The most pronounced peaks in the spectrum have been attributed to np('3)(PI)(,g) (<---) 5s('3)(SIGMA)(,u)('+) (7 (LESSTHEQ) n (LESSTHEQ) 18) transitions. The series limit and quantum defect, (delta), for the np('3)(PI)(,g) series have been determined to be 28471.9 (+OR-) 3.9 cm('-1) (351.12 (+OR-) 0.05 nm) and 2.629 (+OR-) 0.004, respectively. The vibrational frequency, (omega)(,e), of the 5s('3)(SIGMA)(,u)('+) excimer has been estimated to be (TURN) 195 cm('-1). Comparison of the np('3)(PI)(,g) (<---) 5s('3)(SIGMA)(,u)('+) series limit and the ionization potential of Kr* 5s 3/2 (,2) shows that the A('2)(SIGMA)(,u)('+) ground state dimer ion is (TURN) 0.55 eV more deeply bound than the neutral Kr(,2) 5s('3)(SIGMA)(,u)('+). Also, dissociation energies of the ('3)(PI)(,g) Rydbergs are shown to be nearly identical to that of the A('2)(SIGMA)(,u)('+) dimer ion. A second series of spectral peaks has also been identified and assigned to np('3)(SIGMA)(,g)('+) (<---) 5s('3)(SIGMA)(,u)('+) transitions. Analysis of the series yielded a limit of 28424 (+OR-) 120 cm('-1) and a quantum defect of 3.39 (+OR-) 0.04. Absolute cross sections for the np('3)(PI)(,g) (<---) 5s('3)(SIGMA)(,u)('+) (7 (LESSTHEQ) n (LESSTHEQ) 18) transitions have also been determined. In addition, a low resolution photoionization spectrum of Kr(,2) ('3)(SIGMA)(,u)('+) has been obtained and this spectrum is in general agreement with the excitation data as to the ionization potential of the excimer.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Electrical Engineering

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Ediger, Marwood Neal

• Engineering, Electronics and Electrical

Identifier

(UMI)AAI8600167

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/69314