Theoretical Study On The Hydrogen Bond Between Phosphite Ozonide Complexes And Small Molecule Cluster

Study of density functional calculation at B3LYP/6-31+G(d) level provides optimized geometries, transition states of all kinds of phosphite ozonide complexes (CH₃O)₃PO₃.(H₂O)_n(n=1-3),C₂H₅C(CH₂O)₃PO,.(H₂O)_n(n=1.2).C₆H₆OCH₂(CH₂O)₂PO₃.(H₂O)_n(n=1.2).(CH₃O)₃PO₃.(CH₃OH)_n(n=1-2), C₂H₅C(CH₂O)₃PO₃CH₃OH and C₆H₆OCH₂(CH₂O)₂PO₃.CH₃OH. In order to demonstrate the hydrogen bond properties of the complexes. All optimized geometries and transition states were carried by B3LYP/6-311 ++G(d, p) level of theory on the lower-level optimized geometries, as well as the zero point energies(ZPE) were calculated for all structures. The calculation also provided activation energies for the extrusion of singlet oxygen from these complexes and the interaction energies have been compared. We found that the clusters of water molecules would affect the activation energies of these phosphite ozonide complexes remarkablely. When the hydrogen bond were formed between water molecule and cleavage prouduct of singlet oxygen, as well as with the numer of water molecules increasing, the activation energies would depress. Moreover, the effect of one methanol molecule would increase the activation energies, while two methanol molecules would depress the activation energies. Besides that the binding energies between all kinds of complexes would rise with the number of water or methanol molecules increasing, and the hydrogen effect of the methanol molecule are stronger than that of water molecule. While, We have analyzed the difference of parameters and charge distributions due to the effect of the hydrogen bond. We found that all of these changes due to the effect of the hydrogen bond would follow the same rule. The P-O and 0-0 bonds that would brek first would stretch, the new P-O double bond and O-O bond of O₂ would shorten, and the torsional angle would twist strongly. The results of wate rmolecule would suggest that one H-O bond would extend and the other H-O bond would shorten, and then, the flexible vibratile frequence of the H-O bond would reduce (red shift). In addition to, the MO population analysis of the most satable configutatons have been investigated using the ab initio HF/STO-3G. The results demostrate that one of the O-O bonds would bread first, followed by the simultaneous cleavage of one of P-O bonds, with formation of singlet oxygen...