TRIMETHYL PHOSPHATE-WATER INTERACTION - A MATRIX-ISOLATION INFRARED AND AB-INITIO STUDY

Citation
K. Sankaran et al., TRIMETHYL PHOSPHATE-WATER INTERACTION - A MATRIX-ISOLATION INFRARED AND AB-INITIO STUDY, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 102(17), 1998, pp. 2944-2953
Citations number
23
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry Physical
ISSN journal
1089-5639
Volume
102
Issue
17
Year of publication
1998
Pages
2944 - 2953
Database
ISI
SICI code
1089-5639(1998)102:17<2944:TPI-AM>2.0.ZU;2-B
Abstract
Trimethyl phosphate (TMP) and water were co-deposited in nitrogen and argon matrices, and adducts of these species were identified using inf rared spectroscopy. Formation of the adducts was evidenced by shifts i n the vibrational frequencies of TMP and water. We computed the struct ures of these adducts and the vibrational frequencies at the HF/6-31G level. The computed vibrational frequencies in the adducts involving the TMP submolecule compared well with the observed frequencies, whil e the agreement was rather poor for the modes involving the H2O submol ecule. Both experimental and computational studies indicated that two types of TMP-water complexes were formed: one in which the hydrogen in water was bonded to the phosphoryl oxygen of TMP and another in which the bonding was at the alkoxy oxygen of the phosphate. The stabilizat ion energy of these adducts, corrected for zero-point energies and bas is set superposition errors, was computed at both the HF/6-31G*//HF/6 -31G* and MP2/6-31G**//HF/6-31G** levels. Our computations indicated that both the phosphoryl and alkoxy oxygen bonded TMP-H2O complexes ha d a cyclic structure determined by a combination of two hydrogen-bonde d interactions, one involving a hydrogen in water and another involvin g a hydrogen in the methyl group of TMP.