Nuclear quantum effects in the structure and lineshapes of the N2 NEXAFS spectrum

PDF Version Also Available for Download.

Description

We study the relative ability of several models of the X-ray absorption spectrum to capture the Franck-Condon structure apparent from an experiment on gaseous nitrogen. In doing so, we adopt the Born-Oppenheimer approximation and a constrained density functional theory method for computing the energies of the X-ray-excited molecule. Starting from an otherwise classical model for the spectrum, we systematically introduce more realistic physics, first by substituting the quantum mechanical nuclear radial density in the bond separation R for the classical radial density, then by adding the effect of zero-point energy and other level shifts, and finally by including explicit rovibrational ... continued below

Physical Description

9

Creation Information

Fatehi, Shervin; Schwartz, Craig P.; Saykally, Richard J. & Prendergast, David December 4, 2009.

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

We study the relative ability of several models of the X-ray absorption spectrum to capture the Franck-Condon structure apparent from an experiment on gaseous nitrogen. In doing so, we adopt the Born-Oppenheimer approximation and a constrained density functional theory method for computing the energies of the X-ray-excited molecule. Starting from an otherwise classical model for the spectrum, we systematically introduce more realistic physics, first by substituting the quantum mechanical nuclear radial density in the bond separation R for the classical radial density, then by adding the effect of zero-point energy and other level shifts, and finally by including explicit rovibrational quantization of both the ground and excited states. The quantization is determined exactly, using a discrete variable representation. We show that the NEXAFS spectrum can be predicted semiquantiatively within this framework. We also address the possibility of non-trivial temperature dependence in the spectrum. Finally, we show that it is possible to improve the predicted spectrum by using constrained DFT in combination with more accurate potentials.

Physical Description

9

Source

  • Journal Name: THE JOURNAL OF CHEMICAL PHYSICS; Journal Volume: 132; Related Information: Journal Publication Date: 2010

Language

Item Type

Identifier

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

  • Report No.: LBNL-3895E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 988076
  • Archival Resource Key: ark:/67531/metadc1014324

Collections

This article 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 article?

When

Dates and time periods associated with this article.

Creation Date

  • December 4, 2009

Added to The UNT Digital Library

  • Oct. 14, 2017, 8:36 a.m.

Description Last Updated

  • Oct. 17, 2017, 6:23 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

Fatehi, Shervin; Schwartz, Craig P.; Saykally, Richard J. & Prendergast, David. Nuclear quantum effects in the structure and lineshapes of the N2 NEXAFS spectrum, article, December 4, 2009; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc1014324/: accessed December 13, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.