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The experimental design for computing the harmonic and anharmonic force constant matrices of polyatomic molecules

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Sana, M.

The author proposes a numerical approach to estimate the harmonic and anharmonic force constant matrices, assuming one is able to compute analytically the first order derivative vector of the potential energy surface with respect to the internal coordinates. He uses a polynomial least square fit to interpolate this gradient in the stationary point region. The structure of the regression matrix shows that the harmonic force constant matrix may be obtained even for large molecules; the evaluation of the anharmonic contributions request slightly more labour but is possible for 5 to 7 atoms. The author's work is applicable even at the CI level and the number of computations remains small. He uses the experimental planification to select the geometries to be computed in order to improve the estimation of the regression coefficients, i.e. to lower their variance.

Document type Article de périodique (Journal article) – Article de recherche
Access type Accès restreint
Publication date 1982
Journal information "Theoretica Chimica Acta" - Vol. 60, no. 6, p. 543-549 (1982)
Peer reviewed yes
issn 0040-5744
Publication status Publié
Affiliation UCL - Autre
Links
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Bibliographic reference Sana, M.. The experimental design for computing the harmonic and anharmonic force constant matrices of polyatomic molecules. In: Theoretica Chimica Acta, Vol. 60, no. 6, p. 543-549 (1982)
Permanent URL http://hdl.handle.net/2078.1/66479