skip to main content

DOE PAGESDOE PAGES

Title: An exact variational method to calculate vibrational energies of five atom molecules beyond the normal mode approach

We present a full dimensional variational algorithm to calculate vibrational energies of penta-atomic molecules. The quantum mechanical Hamiltonian of the system for J=0 is derived in a set of orthogonal polyspherical coordinates in the body-fixed frame without any dynamical approximation. Moreover, the vibrational Hamiltonian has been obtained in an explicitly Hermitian form. Variational calculations are performed in a direct product discrete variable representation basis set. The sine functions are used for the radial coordinates, whereas the Legendre polynomials are employed for the polar angles. For the azimuthal angles, the symmetrically adapted Fourier–Chebyshev basis functions are utilized. The eigenvalue problem is solved by a Lanczos iterative diagonalization algorithm. The preliminary application to methane is given. Ultimately, we made a comparison with previous results.
Authors:
 [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
OSTI Identifier:
1303029
Report Number(s):
BNL--112549-2016-JA
Journal ID: ISSN 0021-9606; JCPSA6; R&D Project: CO-006; KC0301020
Grant/Contract Number:
SC00112704; AC02-98CH10886
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 117; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS Vibrational spectrum; iterative diagonalization; spectral transform Lanczos method