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Dynamics of Rotationally Resolved Multiphoton Ionization Processes in Molecules

Citation

Rudolph, Henrik (1989) Dynamics of Rotationally Resolved Multiphoton Ionization Processes in Molecules. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/981t-6997. https://resolver.caltech.edu/CaltechTHESIS:08272013-104333878

Abstract

This dissertation presents the results of studies of several rotationally-resolved resonance enhanced multiphoton ionization (REMPI) processes in some simple molecular systems. The objective of these studies is to quantitatively identify the underlying dynamics of this highly state-specific process which utilizes the narrow bandwidth radiation of a laser to ionize a molecule by first preparing an excited state via multiphoton absorption and subsequently ionizing that state before it can decay. Coupled with high-resolution photoelectron spectroscopy, REMPI is clearly an important probe of molecular excited states and their photoioniza tion dynamics.

A key feature of our studies is that they are carried out using accurate Hartree-Fock orbitals to describe the photoelectron orbitals of the molecular ions. The use of such photoelectron orbitals is important in rotationally-resolved studies where the angular momentum coupling in the photoelectron orbital plays a significant role in the photoionization dynamics. In these studies the Hartree-Fock molecular molecular photoelectron orbitals are obtained by numerical solution of a Lippmann-Schwinger integral equation.

Studies reported here include investigations of (i) ionic rotational branching ratios and their energy dependence for REMPI via the A2Σ+(3sσ) and D2Σ+(3pσ)states of NO, (ii) the influence of angular momentum constraints on branching ratios at low photoelectron energies for REMPI via low-J levels of the resonant intermediate state, (iii) the strong dependence of photoelectron angular distributions on final ionic rotational state and on the alignment in REMPI of the A2Σ+ state of NO, (iv) vibrational state dependence of ionic rotational branching ratios arising from rapid orbital evolution in resonant states (E'2Σ+(3pσ) of CH), (v) the influence of rovibronic interactions on the rotational branching ratios seen in REMPI via the D2Σ+(3pσ) state of NO, and (vi) effects of laser intensity on the photoionization dynamics of REMPI.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • McKoy, Basil Vincent
Thesis Committee:
  • Zewail, Ahmed H. (chair)
  • McKoy, Basil Vincent
  • Bercaw, John E.
  • Okumura, Mitchio
Defense Date:15 May 1989
Record Number:CaltechTHESIS:08272013-104333878
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:08272013-104333878
DOI:10.7907/981t-6997
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/0009-2614(87)80622-XDOIArticle adapted for Chapter 1.
https://doi.org/10.1063/1.454191DOIArticle adapted for Chapter 2.
https://doi.org/10.1063/1.455953DOIArticle adapted for Chapter 3.
https://doi.org/10.1063/1.457031DOIArticle adapted for Chapter 4.
https://doi.org/10.1063/1.457424DOIArticle adapted for Chapter 5.
https://doi.org/10.1063/1.457161DOIArticle adapted for Chapter 6.
https://doi.org/10.1063/1.452174DOIArticle adapted for Chapter 7.
https://doi.org/10.1063/1.450718DOIArticle adapted for Chapter 8.
https://doi.org/10.1063/1.454130DOIArticle adapted for Chapter 9.
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7947
Collection:CaltechTHESIS
Deposited By:INVALID USER
Deposited On:27 Aug 2013 18:19
Last Modified:20 Oct 2021 00:02

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