Matrix‐Isolated Hydrogen‐Bonded and Van der Waals Complexes of Hydrogen Peroxide with OCS and CS₂

Abstract

Matrix isolation spectroscopy has been combined with ab initio calculations to characterize the 1:1 complexes of H2O2 with OCS and CS2. The infrared spectra of the argon and nitrogen matrices doped with H2O2 and OCS or CS2 have been measured and analyzed. The geometries of the complexes were optimized at the MP2/6-311++G(3df,3pd) level of theory. Four structures were found for the OCS-H2O2 complex and five for the CS2-H2O2 one; every pair of the corresponding structures showed close correspondence. For every optimized structure the interaction energy was partitioned according to the SAPT Scheme and the topological distribution of the charge density (AIM theory) was performed. The SAPT analysis and AIM results indicate that only one complex among the nine optimized ones is stabilized by the hydrogen bonding, namely the OCS-H2O2 one with the OH group of H2O2 bonded to an oxygen atom of OCS. The other structures are stabilized by van der Waals interaction. The spectra analysis evidences that at least two types of the complexes are trapped in the argon matrices including the most stable ones: hydrogen bonded structure in the case of the OCS-H2O2 complex and the structure stabilized by the S···H and C···O interactions in the case of the CS2-H2O2 complex. The solid nitrogen environment triggers the formation of the structures of C2v symmetry with a sulfur atom of OCS or CS2 directed toward the center of O-O bond of H2O2, stabilized by S···O interactions.

The OH-Initiated Oxidation of CS2in the Presence of NO: FTIR Matrix-Isolation and Theoretical Studies

“…Group I involves sharp strong band at 2059.4 and a weaker one at 2049.7 with a shoulder at 2052.3 cm –1 . On the basis of literature data , and our earlier studies the 2049.7 cm –1 band can be safely assigned to the ν­(CO) vibration of OCS. The performed experiments with 13 CS 2 /HONO/Ar matrices confirm this assignment.…”

Elucidating the interaction of H 2 O 2 with polar amino acids – Quantum chemical calculations

“…A few quantum chemical calculations have been performed on the interaction of H 2 O 2 with glycine [30], uracil [31], adenine [32], urea [33], phenol [34] and serine [35]. Theoretical investigations of H 2 O 2 binding with water cluster [36] and small molecules, e.g., methyl halides [37], NH 2 NO [38], OCS, CS 2 [39], hydrogen halides [40] and several ions, e.g., F − , Cl − , Br − , Li + and Na + [41], have also been investigated. However, despite the immense interest on H 2 O 2 in biological systems, to the best of our knowledge, there has been no systematic investigation focusing on the interaction between amino acid side chains and H 2 O 2 .…”

Theoretical Investigation on H2O2-Ng (He, Ne, Ar, Kr, Xe, and Rn) Complexes Suitable for Stereodynamics: Interactions and Thermal Chiral Rate Consequences

“…These features indicate that HP should be a better proton donor for hydrogen bonding than water. Thus, the understanding of how the relative orientation of the O-H can lead to a weakly complex or a chemical reaction has also been paid considerable attention due to its implication in atmospheric chemistry and oxidation reactions (Lundell et al, 1998, 2001; Daza et al, 2000; Goebel et al, 2000, 2001a,b, 2002; Molina et al, 2002; Pehkonen et al, 2004; Mucha and Mielke, 2009; Grzechnik et al, 2013). Moreover, HP's properties have been investigated, such as its isolated chirality (Roncaratti and Aquilanti, 2010), stereomutation (Fehrensen et al, 2007; Bitencourt et al, 2008), size-dimensional wave packets (Wang et al, 2012), spectroscopy (Hunt et al, 1965; Małyszek and Koput, 2013; Al-Refaie et al, 2015) and rotation barriers (Song et al, 2005).…”