JOURNAL ARTICLE

Computational investigation of the vibrational and electronic states of S2N2

Adam J Bridgeman, Beth Cunningham
Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy 2004, 60 (1): 471-80
14670515
The structures and vibrational frequencies of the ground and excited states of S(2)N(2) have been calculated using density functional (DF) methods. Time-dependent DF theory (TDDFT) has been used to calculate the excitation energies of the lowest 20 singlet-singlet transitions using a variety of methods. All computational methods predict a small highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. There is some disagreement in the ordering of the b(2g) and b(3g) pi orbitals. This is reflected in the ordering of the B(2u) and B(3u) states from the TDDFT calculations. The excitation energies and oscillator strengths strongly suggest it is the transitions to these states that are responsible for the experimental electronic spectrum. The calculated geometries and vibrational frequencies for these two states show that both have C(2v) equilibrium structures. Modelling of the vibrational progressions and band shapes suggest that the ordering of the states is B(2u)<B(3u). Bond order calculations indicate significant S-S pi bonding in the ground state and that this is enhanced in the B(2u) excited state. The geometry of this state distorts by folding of the planar ring to increase the trans-annular S-S bonding.

Full Text Links

Find Full Text Links for this Article

Discussion

You are not logged in. Sign Up or Log In to join the discussion.

Related Papers

Remove bar
Read by QxMD icon Read
14670515
×

Save your favorite articles in one place with a free QxMD account.

×

Search Tips

Use Boolean operators: AND/OR

diabetic AND foot
diabetes OR diabetic

Exclude a word using the 'minus' sign

Virchow -triad

Use Parentheses

water AND (cup OR glass)

Add an asterisk (*) at end of a word to include word stems

Neuro* will search for Neurology, Neuroscientist, Neurological, and so on

Use quotes to search for an exact phrase

"primary prevention of cancer"
(heart or cardiac or cardio*) AND arrest -"American Heart Association"