Density functional study of the S0 (X1Ag) and T1 (a3Au) states of the glyoxal molecule

ABSTRACT

The density functional theory (DFT) calculations in different approximations have been performed for the geometries and vibrational states of the trans-glyoxal molecule in the ground state S0 (X1Ag) and in the lowest excited triplet state T1 (a3Au, n-pi* type). Eight typical combinations of exchange and correlation functionals have been used. Comparative Hartree-Fock (HF) calculations have also been performed. For the open shell a3Au state the standard spin-unrestricted Hartree-Fock and Kohn-Sham approaches (UHF, UKS) as well as the restricted open-shell versions (ROHF, ROKS) have been applied. The calculated frequencies have been compared, among others, with the data resulting from the most recent phosphorescence exicitation spectra of glyoxal cooled in the supersonic molecular beam, recorded with the cooperation of one of us (JH) for the spin-forbidden S0-T1 transition. The most realistic description of the vibrational frequencies, within the unscaled harmonic approximation, can be obtained using the 3-parameter Becke-93 exchange functional (B3), whereas this description practically does not depend on the correlation functional used. Our calculations support the recently reexamined experimental energy of the symmetric CH-rocking fundamental for the T1 state.