Calculation of the Resonance Raman Intensities of Nickel bis-Dimethylglyoxime by means of Density Functional Theory and the Transform Theory

Article type: Research Article

Authors: Mroginski, Maria-Andrea^{a; b; 1} | Mark, Franz^{a; b; 2; 3} | Hildebrandt, Peter^{a; b; 4}

Affiliations: [a] Max-Planck-Institut für Strahlenchemie, Stiftstr. 34–36, D-45470 Mülheim an der Ruhr, Germany | [b] Instituto de Tecnologia Quimica e Biologica, UNL, Apt. 127, P-2780-901 Oeiras, Portugal

Correspondence: [3] Corresponding author

Note: [1] [email protected].

Note: [2] [email protected].

Note: [4] [email protected].

Abstract: The resonance Raman (RR) spectra of nickel bis-dimetliylglyoxime (NiDMG) were calculated in the framework of the transform theory of RR scattering by means of the Rush and Peticolas approximation in combination with density functional theory (DFT). The 11Bu and 11Au excited state geometries, required by this approach, were optimised within time-dependent DFT at the B3LYP and B3P86 levels of theory, using a Newton-Raphson algorithm where the first and second derivatives of the molecular excited state energies were calculated numerically through finite difference approximations. The B3LYP ground state force field was scaled with a set of global scaling factors that correct for errors arising from the quantum chemical method and the harmonic approximation. Comparison between the experimental RR spectra of NiDMG obtained with 413 nm excitation and those calculated in resonance with the transitions to the 11Bu and 11Au states show a good agreement for the most intense RR bands.

Keywords: Resonance Raman intensity, transition metal complex, time-dependent density functional theory, excited state geometry

DOI: 10.3233/JCM-2002-23-415

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 2, no. 3-4, pp. 405-410, 2002