New methods for quantum mechanical reaction dynamics

PDF Version Also Available for Download.

Description

Quantum mechanical methods are developed to describe the dynamics of bimolecular chemical reactions. We focus on developing approaches for directly calculating the desired quantity of interest. Methods for the calculation of single matrix elements of the scattering matrix (S-matrix) and initial state-selected reaction probabilities are presented. This is accomplished by the use of absorbing boundary conditions (ABC) to obtain a localized (L{sup 2}) representation of the outgoing wave scattering Green`s function. This approach enables the efficient calculation of only a single column of the S-matrix with a proportionate savings in effort over the calculation of the entire S-matrix. Applying this ... continued below

Physical Description

178 p.

Creation Information

Thompson, W.H. December 1, 1996.

Context

This thesis or dissertation is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this document can be viewed below.

Who

People and organizations associated with either the creation of this thesis or dissertation or its content.

Author

  • Thompson, W.H. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

Sponsor

Publisher

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this thesis or dissertation. Follow the links below to find similar items on the Digital Library.

Description

Quantum mechanical methods are developed to describe the dynamics of bimolecular chemical reactions. We focus on developing approaches for directly calculating the desired quantity of interest. Methods for the calculation of single matrix elements of the scattering matrix (S-matrix) and initial state-selected reaction probabilities are presented. This is accomplished by the use of absorbing boundary conditions (ABC) to obtain a localized (L{sup 2}) representation of the outgoing wave scattering Green`s function. This approach enables the efficient calculation of only a single column of the S-matrix with a proportionate savings in effort over the calculation of the entire S-matrix. Applying this method to the calculation of the initial (or final) state-selected reaction probability, a more averaged quantity, requires even less effort than the state-to-state S-matrix elements. It is shown how the same representation of the Green`s function can be effectively applied to the calculation of negative ion photodetachment intensities. Photodetachment spectroscopy of the anion ABC{sup -} can be a very useful method for obtaining detailed information about the neutral ABC potential energy surface, particularly if the ABC{sup -} geometry is similar to the transition state of the neutral ABC. Total and arrangement-selected photodetachment spectra are calculated for the H{sub 3}O{sup -} system, providing information about the potential energy surface for the OH + H{sub 2} reaction when compared with experimental results. Finally, we present methods for the direct calculation of the thermal rate constant from the flux-position and flux-flux correlation functions. The spirit of transition state theory is invoked by concentrating on the short time dynamics in the area around the transition state that determine reactivity. These methods are made efficient by evaluating the required quantum mechanical trace in the basis of eigenstates of the Boltzmannized flux operator.

Physical Description

178 p.

Notes

INIS; OSTI as DE97007353

Source

  • Other Information: TH: Thesis (Ph.D.)

Language

Identifier

Unique identifying numbers for this document in the Digital Library or other systems.

  • Other: DE97007353
  • Report No.: LBNL--40238
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 503469
  • Archival Resource Key: ark:/67531/metadc694220

Collections

This document is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

Office of Scientific and Technical Information (OSTI) is the Department of Energy (DOE) office that collects, preserves, and disseminates DOE-sponsored research and development (R&D) results that are the outcomes of R&D projects or other funded activities at DOE labs and facilities nationwide and grantees at universities and other institutions.

What responsibilities do I have when using this thesis or dissertation?

When

Dates and time periods associated with this thesis or dissertation.

Creation Date

  • December 1, 1996

Added to The UNT Digital Library

  • Aug. 14, 2015, 8:43 a.m.

Description Last Updated

  • April 5, 2016, 10:22 a.m.

Usage Statistics

When was this document last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 4

Interact With This Thesis Or Dissertation

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Thompson, W.H. New methods for quantum mechanical reaction dynamics, thesis or dissertation, December 1, 1996; California. (digital.library.unt.edu/ark:/67531/metadc694220/: accessed October 22, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.