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Matrix Isolation and Ab Initio Study of the Hydrogen‐Bonded H 2 O 2 –CO Complex
Author(s) -
Lundell Jan,
Jolkkonen Santtu,
Khriachtchev Leonid,
Pettersson Mika,
Räsänen Markku
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010417)7:8<1670::aid-chem16700>3.0.co;2-n
Subject(s) - matrix isolation , chemistry , ab initio , hydrogen bond , infrared spectroscopy , ab initio quantum chemistry methods , hydrogen , matrix (chemical analysis) , infrared , computational chemistry , photodissociation , crystallography , molecule , photochemistry , physics , organic chemistry , chromatography , optics
The structure, energetics, and infrared spectrum of the H 2 O 2 –CO complex have been studied computationally with the use of ab initio calculations and experimentally by FTIR matrix isolation techniques. Computations predict two stable conformations for the H 2 O 2 –CO complex, both of which show almost linear hydrogen bonds between the subunits. The carbon‐attached HOOH–CO complex is the lower‐energy form, and it has an interaction energy of −9.0 kJ mol −1 at the CCSD(T)/6‐311++G(3df,3pd)//MP2/6‐311++G(3df,3pd) level. The higher‐energy form, HOOH–OC, has an interaction energy of −4.7 kJ mol −1 at the same level of theory. Experimentally, only the lower‐energy form, HOOH–CO, was observed in Ar, Kr, and Xe matrices, and the hydrogen bonding results in substantial perturbations of the observed vibrational modes of both complex subunits. UV photolysis of the complex species primarily produces a complex between water and carbon dioxide, but minor amounts of HCO and trans ‐HOCO were found as well.