Dynamics of high-n Rydberg states employed in zero kinetic energy-pulsed field ionization spectroscopy via the F 1Δ2, D 1Π1, and f 3Δ2 Rydberg states of HCl

Abstract

General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. The intensity anomalies in the spin-orbit and rotational branching ratios in the zero kinetic energy pulsed-field ionization ͑ZEKE-PFI͒ spectra via the F 1 ⌬ 2 , D 1 ⌸ 1 , and f 3 ⌬ 2 Rydberg states of HCl have been studied. In general, the branching ratios are observed to depend on three parameters employed in the pulsed field ionization experiment: ͑i͒ the delay time between excitation and ionization; ͑ii͒ the magnitude of the bias electric field; and ͑iii͒ the magnitude of the applied pulsed electric field. The results can be rationalized on the basis of the increasing number of autoionization decay channels that become available to the high-n Rydberg states as each ionization threshold is surpassed. The delay dependence of the ZEKE-PFI spectra via the F 1 ⌬ 2 state has been analyzed in more detail by ab initio calculations. These calculations show that the observed spin-orbit branching ratios can be reproduced thereby giving evidence for a nonexponential decay of the high-n Rydberg states ͑nϷ100͒.

Decay Dynamics of the Predissociating High Rydberg States of NO

“…ZEKE (zero electron kinetic energy) spectroscopy − has provided valuable insight into the dynamics of high atomic and molecular Rydberg states. − In ZEKE spectroscopy, the lifetimes of high Rydberg states have been found to be orders of magnitude longer than what was expected by extrapolating the lifetimes at low n using an n 3 scaling law and extremely sensitive to external perturbations such as an external dc field, an external magnetic field, or the presence of neighboring ions. The role of the external dc field in diluting the coupling strength to the decay channels over the entire l manifold and increasing the lifetime was early on pointed out by Bordas and Chupka , and then studied in more detail. − The lifetimes of high molecular Rydberg states are also considerably enhanced by collisional effects and the presence of a magnetic field. ,,,− Moreover, experimentally, the decay kinetics of the ZEKE intensity very often exhibits a bimodal character, ,, with a prompt and a delayed component.…”

“…ZEKE (zero electron kinetic energy) spectroscopy [1][2][3][4][5][6][7][8][9][10][11] has provided valuable insight into the dynamics of high atomic and molecular Rydberg states. [12][13][14][15][16][17][18][19][20][21][22][23][24] In ZEKE spectroscopy, the lifetimes of high Rydberg states have been found to be orders of magnitude longer than what was expected by extrapolating the lifetimes at low n using an n 3 scaling law and extremely sensitive to external perturbations such as an external dc field, an external magnetic field, or the presence of neighboring ions. The role of the external dc field in diluting the coupling strength to the decay channels over the entire l manifold and increasing the lifetime was early on pointed out by Bordas 25 and Chupka 26,27 and then studied in more detail.…”

Role of Core Interactions and External Perturbations in the Autoionization of Xe

“…The interpretation of experimental results therefore requires a careful assessment of the ability of the experiment to distinguish and/or detect with equal sensitivity a range of different lifetimes. The importance of the multiexponential nature of the decay of the initially prepared Rydberg population was also emphasized by Bixon and Jortner , and, recently, by Lefebvre-Brion and collaborators …”

“…The importance of the multiexponential nature of the decay of the initially prepared Rydberg population was also emphasized by Bixon and Jortner 30,31 and, recently, by Lefebvre-Brion and collaborators. 32 In our theoretical NO paper, we developed a Hamiltonian description of the NO molecule, which was based on an adaptation of earlier results obtained by multichannel quantum defect theory (MQDT). 33,34 The results of an MQDT analysis by Fredin et al were used to set up a Hamiltonian describing the coupling among Hund's case d basis states induced by shortrange Rydberg electron-core interactions.…”

Laser photoelectron spectroscopy: spectroscopy and dynamics of excited states in small and medium‐sized molecules

“…Especially for molecules with relatively large rotational constants such as the diatomic hydrides such studies are very informative, because they produce a plethora of information on the dynamics of the photoionization process [17,. With the advent of ZEKE the observation of rotationally resolved PES of small molecules has become a very feasible proposition [ 18, 57,58].…”