TITLE

Three-dimensional infinite order sudden quantum theory for indirect photodissociation processes. Application to the photofragment yield spectrum of NOCl in the region of the T1(13A″) ←S0(11A′) transition. Fragment rotational distributions and thermal averages

AUTHOR(S)
Grinberg, Horacio; Freed, Karl F.; Williams, Carl J.
PUB. DATE
August 1997
SOURCE
Journal of Chemical Physics;8/8/1997, Vol. 107 Issue 6, p1849
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The analytical infinite order sudden (IOS) quantum theory of triatomic photodissociation, developed in paper I, is applied to study the indirect photodissociation of NOCl through a real or virtual intermediate state. The theory uses the IOS approximation for the dynamics in the final dissociative channels and an Airy function approximation for the continuum functions. The transition is taken as polarized in the plane of the molecule; symmetric top wave functions are used for both the initial and intermediate bound states; and simple semiempirical model potentials are employed for each state. The theory provides analytical expressions for the photofragment yield spectrum for producing particular final fragment ro-vibrational states as a function of the photon excitation energy. Computations are made of the photofragment excitation spectrum of NOCl in the region of the T1(13A″) ←S0(11A′) transition for producing the NO fragment in the vibrational states nNO=0, 1, and 2. The computed spectra for the unexcited nNO==0 and excited nNO=2 states are in reasonable agreement with experiment. However, some discrepancies are observed for the singly excited nNO=1 vibrational state, indicating deficiencies in the semiempirical potential energy surface. Computations for two different orientations of the in-plane transition dipole moment produce very similar excitation spectra. Calculations of fragment rotational distributions are performed for high values of the total angular momentum J, a feature that would be very difficult to perform with close-coupled methods. Computations are also made of the thermally averaged rotational energy distributions to simulate the conditions in actual supersonic jet experiments. © 1997 American Institute of Physics.
ACCESSION #
33899297

 

Related Articles

  • Toward substantiation of a problem in the general quantum theory of spectra of polyatomic molecules. Gribov, L. // Optics & Spectroscopy;May2012, Vol. 112 Issue 5, p652 

    Certain basic principles of substantiation of the quantum problem in the theory of spectra of complex molecules are considered. A Schröninger equation is introduced that corresponds to the notion of the molecule as a geometric figure. The equation always reflects an inextricable link between...

  • Electron Momentum Spectroscopy and Its Applications to Molecules of Biological Interest. Feng Wang // AIP Conference Proceedings;11/29/2007, Vol. 963 Issue 1, p54 

    Energy and wave function are the heart and soul of Schrödinger quantum mechanics. Electron momentum spectroscopy (EMS) so far provides the most stringent test for quantum mechanical models (theory, basis sets and the combination of both) through observables such as binding energy spectra and...

  • Remote projection and quantum mirages in STS and STM. Doyen, G.; Drakova, D. // Applied Physics A: Materials Science & Processing;2001, Vol. 72 Issue 8, pS163 

    Abstract. The phenomena of remote projection and quantum mirages are investigated using standard quantum mechanics. The information inherent in delocalized wave functions in the vicinity of the Fermi level, including contributions from localized states, is available wherever the waves propagate...

  • Spectroscopic study of the E 1Σ+g ‘‘shelf’’ state in 7Li2. Bernheim, R. A.; Gold, L. P.; Tomczyk, C. A.; Vidal, C. R. // Journal of Chemical Physics;7/15/1987, Vol. 87 Issue 2, p861 

    The E 1Σ+g ‘‘shelf ’’ state of the 7Li2 molecule was investigated using a pulsed optical optical double resonance technique. The measurements cover the vibrational levels in the range 0≤v≤29 including the shelf region around 13≤v≤15. Molecular...

  • A scaling perspective on quantum energy flow in molecules. Schofield, Sarah A.; Wolynes, Peter G. // Journal of Chemical Physics;1/15/1993, Vol. 98 Issue 2, p1123 

    We present an analysis of quantum energy flow and localization in molecules from the point of view of a scaling approach. This scaling approach is based on earlier scaling theories of Anderson localization in disordered metals. The picture provides a simple general framework for describing both...

  • Rydberg–Klein–Rees potential curves: Error analysis and a correction scheme. Pajunen, Petri // Journal of Chemical Physics;6/15/1990, Vol. 92 Issue 12, p7484 

    The fundamental source of error in the Rydberg–Klein–Rees inversion procedure of diatomic spectroscopy is the first-order phase integral or WKB approximation on which it is based. In this article, errors due to this approximation are analyzed and a simple correction scheme is...

  • (e, 2e) momentum spectroscopic study of the interaction of –CH3 and –CF3 groups with the carbon–carbon triple bond. Goruganthu, R. R.; Coplan, M. A.; Moore, J. H.; Tossell, J. A. // Journal of Chemical Physics;7/1/1988, Vol. 89 Issue 1, p25 

    Relative momentum densities have been measured for the outermost occupied π orbitals of acetylene, propyne, 2-butyne, and perfluoro-2-butyne using the (e, 2e) technique with an improved multiple detector spectrometer. The results, when compared with suitably averaged quantum mechanical...

  • The atom in a molecule: A wave function approach. Rychlewski, Jacek; Parr, Robert G. // Journal of Chemical Physics;2/1/1986, Vol. 84 Issue 3, p1696 

    Given a homonuclear diatomic molecule AB with an even number of electrons N in the state ψ. What is the state of atom A in the molecule? Using the lemma that 〈ψ|HA |ψ>/〈ψ|ψ>≥E0A where HA is the Hamiltonian for atom A only, having NA =N/2 electrons, and E0A is the...

  • Quantizing Geometry or Geometrizing the Quantum? Koch, Benjamin // AIP Conference Proceedings;5/4/2010, Vol. 1232 Issue 1, p313 

    The unsatisfactory status of the search for a consistent and predictive quantization of gravity is taken as motivation to study the question whether geometrical laws coud be more fundamental than quantization procedures. In such an approach the quantum mechanical laws should emerge from the...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics