Photoionization mass spectrometric studies of the isomeric transient species CD sub 2 OH and CD sub 3 O

Journal Article · Sun Sep 15 04:00:00 EDT 1991 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.460758· OSTI ID:5333071

Ruscic, B; Berkowitz, J ^[1]

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1. Chemistry Division, Argonne National Laboratory, Argonne, Illinois (USA)

Both CD{sub 2}OH and CD{sub 3}O were prepared {ital in} {ital situ} by the reaction of F atoms with CD{sub 3}OH, and studied by photoionization mass spectrometry. The adiabatic ionization potential (I.P.) of CD{sub 2}OH was found to be 7.540{plus minus}0.006 eV, in good agreement with the photoelectron spectroscopy (PES) value, 7.55{plus minus}0.01 eV. However, the adiabatic I.P. of CD{sub 3}O was determined to be 10.726{plus minus}0.008 eV, in marked contrast to the PES value for CH{sub 3}O, 7.37{plus minus}0.03 eV, but in the expected range based on reported values of {Delta}{ital H}{sup 0}{sub {ital f}}(CH{sub 3}O{sup +}) and {Delta}{ital H}{sup 0}{sub {ital f}}(CH{sub 3}O). From selected values of {Delta}{ital H}{sup 0}{sub {ital f}0}(CH{sub 2}OH{sup +}) {le}172.0{plus minus}0.7 kcal/mol and {Delta}{ital H}{sup 0}{sub {ital f}0}(CH{sub 3}O) =5.9{plus minus}1.0 kcal/mol, we deduce {Delta}{ital H}{sup 0}{sub {ital f}0}(CH{sub 2}OH) {le}{minus}2.1{plus minus}0.7 kcal/mol and {Delta}{ital H}{sup 0}{sub {ital f}0}(CH{sub 3}O{sup +}) =253.1{plus minus}1.0 kcal/mol.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5333071
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 95:6; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AFFINITY
ALCOHOLS
DEUTERIUM COMPOUNDS
ENTHALPY
ETHERS
FORMATION HEAT
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
IONIZATION
IONIZATION POTENTIAL
ISOMERS
ISOTOPE EFFECTS
LIFETIME
MASS SPECTROSCOPY
METHANOL
METHYL ETHER
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOIONIZATION
PHYSICAL PROPERTIES
REACTION HEAT
SPECTROSCOPY
THERMODYNAMIC PROPERTIES