Post on 25-Aug-2020
Free Electron Laser for Infrared eXperiments "FELIX"Free Electron Laser for Infrared eXperiments "FELIX"
FEL-25 - 30
spectrometermagnet
OTRμm
Undulator
25-45 MeV15-25 MeV
FEL-1
Linac 1 Linac 2
16 - 250
injector
μm
Undulator
16 - 250μm
Principles of FTICR-MS
-charged particles trapped by strong, homogeneous magnetic field B (Lorentz force)- particles orbit magnetic field with frequency dependent only on m/z (for fixed B)- trapped particles are confined axially by small static voltage to trapping plates (T)- applying RF to excite plates (E) at cyclotron frequency bunches ions and expands their orbital radii, improving dynamic range also used to eject unwanted ions- current induced by moving ions is detected (D) and amplified in time domain, then Fourier Transformed to obtain frequencies of trapped ions
Cyclotron frequencyf B /f ~ Bz/m
Anionic Metal Carbonyl Clustering Reactions
3.e+0
4.5e+0s\doug\My Documents\FTICR files from FOM\030825-007_Fe2CO8-_PV_p=1e6_8avg_FEL
A
m
p
FELIX off
0.e+0
1.5e+0
354705 359822 364939 370056 375173
l
i
t
u
d
e
54Fe56Fe(CO)8-
off
354705 359822 364939 370056 375173Frequency (Hz)
4.3e+0doug\My Documents\FTICR files from FOM\030825-013_Fe2CO8-_PV_p=1e6_10avg_FEL
A
m FELIX on
0 e+0
1.4e+0
2.9e+0p
l
i
t
u
d
e
o4.76μm
3.2e+0doug\My Documents\FTICR files from FOM\030825-008_Fe2CO8-_PV_p=1e6_10avg_FEL
0.e+0354910 359976 365042 370107 375173
Frequency (Hz)
1.1e+0
2.1e+0
A
m
p
l
i
t
u
d
e
FELIX on 5.12μm
56Fe2(CO)7-
0.e+0354880 359963 365046 370129 375212
Frequency (Hz)
m1008 [Fe8(CO)20- ?]
0.9
1.0
0.90
0.95
1.00
0.80
0.85
0.90
0.95
1.00
m896 [Fe7(CO)18- ?]
m952 [Fe9(CO)16- ?]
0.6
0.7
0.8
0.9
SORI up to higher masses
• By adding additional frequencies to
plet
ion
Fe (CO) -0.95
1.00
0.85
0.90
0.95
1.00
Fe5(CO)14-
• By adding additional frequencies to the SORI excitation pulse, larger and larger cluster can be synthesized• In each case, a large percentage (40-
rmal
ized
dep
1.0
Fe4(CO)13
Fe4(CO)12-
0.85
0.90
0.95
1.00
0.85
0.90100%) of the ion population is transferred into the target mass channel• Spectra show a blue shift with increasing size, converging to a value
Nor
0.7
0.8
0.9
1.0
Fe2(CO)8-
0.7
0.8
0.9
Fe3(CO)10-
increasing size, converging to a value around 2000 cm-1
• Structure in spectrum also disappears with increasing size -- indication of transition from organometallic
0.95
1.00
Fe2(CO)7-
Fe(CO) -
0.7
0.8
0.9
1.0
0transition from organometallic complexes to metal-cluster-adsorbate systems?
1600 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 21500.85
0.90 Fe(CO)4
Wavenumber (cm-1)
Fe2(CO)8- cluster IRMPD spectrum
E t C l (B3LYP / LACVP+* / 0 965 li f t )
( d )
Expt. vs. Calc. (B3LYP / LACVP+* w/ 0.965 scaling factor)rb
. uni
ts)
Expt. (0 dB) Calc. w/ 12 cm-1
Gaussian conv.
sect
ion
(ar
tion
cros
s s
ve a
bsor
ptR
elat
iv
1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150Wavenumber (cm-1)
IR spectrum of anionic Fe2(CO)7 cluster
IRMPD (0 dB) B3LYP/LACVP+*
(scaled by 0.965) (convoluted
/12 -1 i ) w/12 cm gaussian)
1800 1825 1850 1875 1900 1925 1950 1975 2000 2025 2050Wavenumber (cm-1)
I R M P D s p e c t r a o f a n i o n i c i r o n c a r b o n y l c l u s t e r s
F ( C O ) - ( 6 7 2 ) F e 5 ( C O ) 1 4 ( m 6 7 2 ) F e 4 ( C O ) 1 3
- ( m 5 8 8 ) F e 4 ( C O ) 1 3
- ( m 5 6 0 ) F e 3 ( C O ) 1 0
- ( m 4 4 8 ) F e 2 ( C O ) 8
- ( m 3 3 6 )F e ( C O ) - ( m 3 0 8 ) F e 2 ( C O ) 7 ( m 3 0 8 )
1 7 5 0 1 8 0 0 1 8 5 0 1 9 0 0 1 9 5 0 2 0 0 0 2 0 5 0 2 1 0 0 2 1 5 0W a v e n u m b e r ( c m - 1 )
Theoretical spectrum from pSchaefer’s calculations for D2h unbridged structure. Frequencies lowered by 46 cm-1.
1750 1800 1850 1900 1950 2000 2050 2100 2150Frequency (cm-1)
Theoretical spectrum from Schaefer’s calculations for tetrabridged structure. Average lowered by 40 cm-1and range expanded 10% about average10% about average. Imported from Excel plot
1750 1800 1850 1900 1950 2000 2050 2100 2150Frequency (cm-1)
Theoretical spectrum from Schaefer’s calculations for a dibridged C2h structure. Average lowered by 57Average lowered by 57 cm-1. Imported from Excel plot
1750 1800 1850 1900 1950 2000 2050 2100 2150Frequency (cm-1)
Fe2(CO)8- anion
spectrum
1750 1800 1850 1900 1950 2000 2050 2100 2150
Frequency (cm-1)Theoretical spectrum from Schaefer’s calculations for dibridged C2v structure. Average lowered by 60 cm-1 and range expanded
Frequency (cm )
g pby 10%. Imported from Excel plot
Fe2(CO)7- anion spectrum
Fe2(CO)7 neutral harmonicFe2(CO)7 neutral harmonic frequencies (lowered by 52 cm-1 and expanded by 10% about the average) and intensities from DFT calculations for triply bridgedcalculations for triply bridged structure in ref. 1.
1750 1800 1850 1900 1950 2000 2050 2100 2150F ( 1)Frequency (cm-1)
Fe2(CO)7 neutral tribridged C2v2( )7 g 2vstructure optimized using DFT from ref. 1.
1. Xie, Schaefer and King, JACS, 122, 8746(2000)
Fe2(CO)7- anion spectrum
Fe2(CO)7 neutral harmonicFe2(CO)7 neutral harmonic frequencies (lowered by 52 cm-1 and expanded by 10% about the average) and intensities from DFT calculations for singly bridgedcalculations for singly bridged structure in ref. 1.
1750 1800 1850 1900 1950 2000 2050 2100 2150Frequency (cm-1)
Fe2(CO)7 neutral b id d Cmonobridged C2v
structure optimized using DFT from ref. 1.
1. Xie, Schaefer and King, JACS, 122, 8746(2000)
Fe2(CO)7- anion spectrum
Fe2(CO)7 neutral harmonicFe2(CO)7 neutral harmonic frequencies (lowered by 62 cm-1 and expanded by 10% about the average) and intensities from DFT calculations forcalculations for unsymmetrically doubly bridged structure in ref. 1.
1750 1800 1850 1900 1950 2000 2050 2100 2150Frequency (cm-1)
Fe2(CO)7 neutral asymmetrically dib id d C t t ti i ddibridged Cs structure optimized using DFT from ref. 1.
1. Xie, Schaefer and King, JACS, 122, 8746(2000)