Optical-IR double resonance effect for the rovibronic state of (COF)₂

Abstract

In the present study, a resolved optical-IR double resonance (OIRDR) spectrum was recorded for oxalylfluoride excited to the 4 31 3 21 , ð e A 1 A u Þ0 0 0 single rotational line. Assignment of discrete spectral lines and spectral simulations were done using the statistical model. It was found that in the presence of an IR field at an intermediate power level the decay of oxalylfluoride fluorescence is described by a biexponential function. This effect was explained taking into account the S-T, T-T and T-S dynamics. The observed phenomenon is a direct proof of the T-S transitions induced by internal S-T interactions. We found that NO affects the OIRDR spectrum, increasing the line widths. This effect was explained qualitatively by the VdW complex and cluster formation.

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part IV: Analysis of the absorption spectra of oxalyl fluoride in the gas phase

“…It should be also noted that recently in [13] a set of assumed frequencies for trans-oxalyl fluoride in theà 1 A u andã 3 A u states has been presented, but all of them differ significantly from that found by us (from tens to $ 300 cm À1 ).…”

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

“…These studies have focused mainly on probing the dynamics of (COF) 2 upon excitation to various vibronic and rovibronic levels [3][4][5]. There have been several attempts to characterize the vibrational structure of the S 1 S 0 singlet-singlet and T 1 S 0 singlet-triplet electronic transitions of (COF) 2 [6][7][8].…”