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)