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Quantum functional sensitivity analysis within the log-derivative Kohn variational method for reactive scattering

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.463706· OSTI ID:6905366
;  [1];  [2];  [3];  [4]
  1. Energy and Environment Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States)
  2. Thinking Machines Corp., 245 First Street, Cambridge, Massachusetts 02142-1214 (United States)
  3. Department of Chemistry and Institute for Theoretical Chemistry, University of Texas, Austin, Texas 78712 (United States)
  4. Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States)

A new approach to calculating quantum functional sensitivity maps of transition probabilities is described in this paper. This approach is based on the log-derivative version of the Kohn variational principle and is applied here to the collinear H+H[sub 2] hydrogen exchange reaction. The sensitivity maps provide detailed quantitative information about how variations in the potential energy surface affect the state-to-state transition probabilities. The key issues investigated are (i) the evolution of sensitivity structure in the 0.30--1.50 eV range of total energy; (ii) the comparison of sensitivity structure on the Porter--Karplus, the Liu--Siegbahn--Truhlar--Horowitz, and the double-many-body-expansion potential energy surfaces; and (iii) the range of linearity for first order sensitivity predictions.

DOE Contract Number:
AC03-76SF00098
OSTI ID:
6905366
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 97:9; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English