| Abstract: | A method is proposed to calculate the vibrational structures of the electronic spectra of polyatomic molecules based on the variational solution of the vibrational problem in the excited state with the vibrational wave functions of the ground state as basis set. The electrono-vibrational problem leads to an evaluated and diagonalized variational matrix. The elements of the variational matrix have a simple form which is easily evaluated, has a clear physical meaning and is directly interconnected with observed spectral effects. This allows preliminary estimation of spectral phenomena and correction of the molecular model to take account of experimental results. The use of contemporary methods of diagonalization of the variational matrix, which possesses a characteristic structure, facilitates a tenfold increase in the speed of the method in comparison with traditional methods.K. A. Timiryazev Agricultural Academy. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 1, pp. 141–148, January–February, 1993. |
