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.)) | ||||||||||||||||||||||||||||||
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| Subject Keywords: | Chemistry | ||||||||||||||||||||||||||||||
| Degree Grantor: | California Institute of Technology | ||||||||||||||||||||||||||||||
| Division: | Chemistry and Chemical Engineering | ||||||||||||||||||||||||||||||
| Major Option: | Chemistry | ||||||||||||||||||||||||||||||
| Thesis Availability: | Public (worldwide access) | ||||||||||||||||||||||||||||||
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| Defense Date: | 15 May 1989 | ||||||||||||||||||||||||||||||
| Record Number: | CaltechTHESIS:08272013-104333878 | ||||||||||||||||||||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:08272013-104333878 | ||||||||||||||||||||||||||||||
| DOI: | 10.7907/981t-6997 | ||||||||||||||||||||||||||||||
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| 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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