Semiclassical (SC) Description of Electronically Non-AdiabaticDynamics via the Initial Value Representation (IVR)

PDF Version Also Available for Download.

Description

The initial value representation (IVR) of semiclassical (SC) theory is used in conjunction with the Meyer-Miller/Stock-Thoss description of electronic degrees of freedom in order to treat electronically non-adiabatic processes. It is emphasized that the classical equations of motion for the nuclear and electronic degrees of freedom that emerge in this description are precisely the Ehrenfest equations of motion (the force on the nuclei is the force averaged over the electronic wavefunction), but that the trajectories given by these equations of motion do not have the usual shortcomings of the traditional Ehrenfest model when they are used within the SC-IVR framework. ... continued below

Creation Information

Ananth, V.; Venkataraman, C. & Miller, W.H. June 22, 2007.

Context

This article 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 article can be viewed below.

Who

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

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 article. Follow the links below to find similar items on the Digital Library.

Description

The initial value representation (IVR) of semiclassical (SC) theory is used in conjunction with the Meyer-Miller/Stock-Thoss description of electronic degrees of freedom in order to treat electronically non-adiabatic processes. It is emphasized that the classical equations of motion for the nuclear and electronic degrees of freedom that emerge in this description are precisely the Ehrenfest equations of motion (the force on the nuclei is the force averaged over the electronic wavefunction), but that the trajectories given by these equations of motion do not have the usual shortcomings of the traditional Ehrenfest model when they are used within the SC-IVR framework. For example, in the traditional Ehrenfest model (a mixed quantum-classical approach) the nuclear motion emerges from a non-adiabatic encounter on an average potential energy surface (a weighted average according to the population in the various electronic states), while the SC-IVR describes the correct correlation between electronic and nuclear dynamics, i.e., the nuclear motion is on one potential energy surface or the other depending on the electronic state. Calculations using forward-backward versions of SC-IVR theory (FB-IVR) are presented to illustrate this behavior. An even more approximate version of the SC-IVR, the linearized approximation (LSC-IVR), is slightly better than the traditional Ehrenfest model, but since it cannot describe quantum coherence effects, the LSC-IVR is also not able to describe the correct correlation between nuclear and electronic dynamics.

Source

  • Journal Name: Journal of Chemical Physics; Journal Volume: 127; Related Information: Journal Publication Date: 2007

Language

Item Type

Identifier

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

  • Report No.: LBNL--63541
  • Grant Number: AC02-05CH11231
  • DOI: 10.1063/1.2759932 | External Link
  • Office of Scientific & Technical Information Report Number: 918937
  • Archival Resource Key: ark:/67531/metadc890000

Collections

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

Office of Scientific & Technical Information Technical Reports

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • June 22, 2007

Added to The UNT Digital Library

  • Sept. 22, 2016, 2:13 a.m.

Description Last Updated

  • Sept. 29, 2016, 6:59 p.m.

Usage Statistics

When was this article last used?

Congratulations! It looks like you are the first person to view this item online.

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Ananth, V.; Venkataraman, C. & Miller, W.H. Semiclassical (SC) Description of Electronically Non-AdiabaticDynamics via the Initial Value Representation (IVR), article, June 22, 2007; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc890000/: accessed August 22, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.