Document Detail


Progress in calculating the potential energy surface of H3+.
MedLine Citation:
PMID:  23028149     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
The most accurate electronic structure calculations are performed using wave function expansions in terms of basis functions explicitly dependent on the inter-electron distances. In our recent work, we use such basis functions to calculate a highly accurate potential energy surface (PES) for the H(3)(+) ion. The functions are explicitly correlated Gaussians, which include inter-electron distances in the exponent. Key to obtaining the high accuracy in the calculations has been the use of the analytical energy gradient determined with respect to the Gaussian exponential parameters in the minimization of the Rayleigh-Ritz variational energy functional. The effective elimination of linear dependences between the basis functions and the automatic adjustment of the positions of the Gaussian centres to the changing molecular geometry of the system are the keys to the success of the computational procedure. After adiabatic and relativistic corrections are added to the PES and with an effective accounting of the non-adiabatic effects in the calculation of the rotational/vibrational states, the experimental H(3)(+) rovibrational spectrum is reproduced at the 0.1 cm(-1) accuracy level up to 16,600 cm(-1) above the ground state.
Authors:
Ludwik Adamowicz; Michele Pavanello
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Philosophical transactions. Series A, Mathematical, physical, and engineering sciences     Volume:  370     ISSN:  1364-503X     ISO Abbreviation:  Philos Trans A Math Phys Eng Sci     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-10-02     Completed Date:  2012-11-13     Revised Date:  2013-04-24    
Medline Journal Info:
Nlm Unique ID:  101133385     Medline TA:  Philos Trans A Math Phys Eng Sci     Country:  England    
Other Details:
Languages:  eng     Pagination:  5001-13     Citation Subset:  -    
Affiliation:
Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA.
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