Nonempirical anharmonic vibrational perturbation theory applied to biomolecules: free-base porphin

Anharmonic vibrational frequencies and intensities (infrared and Raman) of an isolated free-base porphin molecule are predicted from the quantum mechanical (QM) geometry, the "semi-diagonal" quartic force field, and dipole moment and polarizability surfaces. The second-order vibrational perturbation theory plus the numerical diagonalization of the Hamiltonian matrix containing off-diagonal Fermi and Darling-Dennison resonance couplings (VPT2+WK) was used. The QM calculations were carried out with the Becke-Lee-Yang-Parr composite exchange-correlation functional (B3LYP) and with the 6-31+G(d,p) basis set. The harmonic force field for the equilibrium configuration was transformed into nonredundant local symmetry internal coordinates, and normal coordinates were defined. The semi-diagonal quartic rectilinear normal coordinate potential energy surface (PES), as well as the cubic surfaces of dipole moment (p) and polarizability (α) components, needed for the VPT2+WK calculation, were constructed by a five-point finite differentiation of Hessians (for PES) and of the values and first derivatives of p and α. They were obtained at the point of equilibrium and for 432 displaced configurations. This theoretical approach provides very good agreement between the predicted and experimental frequencies and intensities. However, the favorable result can be partly attributed to error cancellation within the B3LYP/6-31+G(d,p) QM model, as observed in earlier studies. Reassignments of some observed bands are proposed.