IO(X²Π)–Ar cluster: ab initio potential energy surface and dynamical computations

Abstract

Spectroscopic and dynamical characterisation of IO–Ar cluster.

Theoretical treatment of IO–X (X = N2, CO, CO2, H2O) complexes

“…Nevertheless, it is commonly established that the electronic orbital angular momentum and the electron spin in the IO–X species have well-defined projections onto the internuclear axis, resulting in two spin–orbit manifolds, which can be treated separately. 28 This is confirmed by the spin–orbit results detailed above. Also, bent structures can be treated without the consideration of the Renner–Teller effect and spin–orbit interactions since the latter induce small perturbations of their rovibronic spectra.…”

“…At the RCCSD(T)/CBS, we compute BEs (in kcal mol À1 ) of À1.541 for OI-N 2 and À0.768 for IO-N 2 , of À1.260 for OI-CO and of À1.051 for IO-CO, of À2.079 for OI-CO 2 and À1.974 for IO-CO 2 , and of À4.991 for OI-H 2 O and À2.738 for IO-H 2 O. The presently found over stability of the halogen bonded complexes vs. the hydrogen bonded complexes was already noticed for IO-Ar, 28 for monohydrates of IO, 34,59 of ClO, 72 of BrO, 72 of INO, 73 and of INO 2 , 73 for hypoiodous acid interacting with CO (i.e. HOI-CO) 74 and for hypoiodous acid interacting with NH 3 (i.e.…”

“…large basis sets and advanced configuration interaction approaches. 28,84 Table 1 shows that OI-N 2 and OI-CO are linear. They possess thus 5 vibrational modes: 3 stretchings (of s symmetry) and 2 doubly degenerate bendings (of p symmetry).…”

“…Both modelling 25 and experimental 26,27 studies are performed to elucidate, for instance, the role of IO in the tropospheric oxidation of iodine-containing species. These works allowed us to determine the structural, energetic and thermodynamic properties of the reactive and/or non-reactive collisions between IO and the following compounds: Ar, 28 ClO, 29 BrO, 29 CF 3 O, 30 NH 2 , 31 CO, 32,33 H 2 O, 34 IO, 34 OIO, 34 HNO 3 , 35 NO, 36 O 3 , 37 NO 3 , 38 and HO 2 . 39 In particular, they showed that the first steps of such possesses correspond to the formation of weakly bound complexes between IO and these molecules.…”

Vibrational description of the LiAr molecule in its X 2Σ+ and A 2Π electronic states in the framework of an algebraic model

“…One of the potential methodologies to alleviate the exactness of the targeted systems is to start by testing these novel approaches on the alkali and rare gas molecules. Indeed, theses interactions have gained substantial attention due to the features of the noble gasses related to their closed valence shells that render them tractable as model systems [10]. Consequently, these molecules can be investigated theoretically using semi-empirical calculations since core and valence electrons can be treated independently [5,11].…”