TY - JOUR
T1 - Dissociative charge transfer of singly- and doubly-charged rare gas ions with W(CO)6
AU - Horning, Stevan R.
AU - Kotiaho, Tapio
AU - Dejarme, Lindy E.
AU - Wood, Joe M.
AU - Cooks, R. Graham
PY - 1991
Y1 - 1991
N2 - Charge exchange of the thermometer compound, W(CO)6, with singly-charged rare gas ions yields internally excited W(CO)+6 molecular ions. The internal energy distribution, P(ε),
of the nascent ions is estimated by an approximate thermochemical
method which is based on dissociation by successive CO losses. The
average internal energy agrees well with expectation based on the known
values of the rare gas recombination energies. The distribution of
internal energies have half widths of 1–3 eV and maxima which correspond
to the calculated heats of reaction. Energy deposition is only a weak
function of collision energy, increasing by a few tenths of an
electronvolt in the range 2.5–10 eV, and then remaining constant to 30
eV. Singly-charged argon and neon ions, but not the other singly-charged
rare gas ions, show production of doubly-charged metal carbonyls due to
contributions from Ar+ and Ne+ in long-lived excited states.Charge exchange of W(CO)6 with the doubly-charged rare gas
ions shows three prominent processes: (i) single-electron transfer,
which is accompanied by average internal energy depositions as high as
15 eV and gives products with wider and more asymmetric internal energy
distributions than those which occur by charge exchange with the
singly-charged rare gas ions; (ii) double-electron transfer to generate
doubly- charged tungsten hexacarbonyl ions, W(CO)2+n and WC(CO)2+n; and (iii) the formation of unexcited W(CO)+6 ions resulting from charge exchange between the nascent doubly-charged ion and neutral W(CO)6. The maxima of the P(ε)
curves for both single and doubel electron transfer agree with
thermo-chemical predictions except that there is a small, systematic,
difference in energy deposition for the single-electron transfer process
which is ascribed to mutual coulombic repulsion of the products.
Doubly-charged neon yields both ground state and excited state Ne+.
The average internal energies for both single- and double-electron
transfer are almost independent of the laboratory collision energy,
indicating that long-range electron transfer is involved.
AB - Charge exchange of the thermometer compound, W(CO)6, with singly-charged rare gas ions yields internally excited W(CO)+6 molecular ions. The internal energy distribution, P(ε),
of the nascent ions is estimated by an approximate thermochemical
method which is based on dissociation by successive CO losses. The
average internal energy agrees well with expectation based on the known
values of the rare gas recombination energies. The distribution of
internal energies have half widths of 1–3 eV and maxima which correspond
to the calculated heats of reaction. Energy deposition is only a weak
function of collision energy, increasing by a few tenths of an
electronvolt in the range 2.5–10 eV, and then remaining constant to 30
eV. Singly-charged argon and neon ions, but not the other singly-charged
rare gas ions, show production of doubly-charged metal carbonyls due to
contributions from Ar+ and Ne+ in long-lived excited states.Charge exchange of W(CO)6 with the doubly-charged rare gas
ions shows three prominent processes: (i) single-electron transfer,
which is accompanied by average internal energy depositions as high as
15 eV and gives products with wider and more asymmetric internal energy
distributions than those which occur by charge exchange with the
singly-charged rare gas ions; (ii) double-electron transfer to generate
doubly- charged tungsten hexacarbonyl ions, W(CO)2+n and WC(CO)2+n; and (iii) the formation of unexcited W(CO)+6 ions resulting from charge exchange between the nascent doubly-charged ion and neutral W(CO)6. The maxima of the P(ε)
curves for both single and doubel electron transfer agree with
thermo-chemical predictions except that there is a small, systematic,
difference in energy deposition for the single-electron transfer process
which is ascribed to mutual coulombic repulsion of the products.
Doubly-charged neon yields both ground state and excited state Ne+.
The average internal energies for both single- and double-electron
transfer are almost independent of the laboratory collision energy,
indicating that long-range electron transfer is involved.
U2 - 10.1016/0168-1176(91)80015-F
DO - 10.1016/0168-1176(91)80015-F
M3 - Article
SN - 0168-1176
VL - 110
SP - 1
EP - 29
JO - International Journal of Mass Spectrometry and Ion Processes
JF - International Journal of Mass Spectrometry and Ion Processes
IS - 1-2
ER -