Charge Reversal Fourier Transform Ion Cyclotron Resonance
Mass Spectrometry
Vladislav V. Lobodin1, Joshua J. Savory1, Nathan K. Kaiser1, Paul W. Dunk2, and
Alan G. Marshall1,2
1
2
National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive, Tallahassee, FL 32310, USA
Florida State University, Department of Chemistry and Biochemistry, 95 Chieftain Way, Tallahassee, FL
32306, USA
Supporting Information
1
Table S1. Elemental composition assignments for charge reversal ions from 3,3’bicarbazole.
m/z
333.1297
332.1263
332.1218
331.1230
331.1186
331.1142
330.1153
330.1108
329.1074
329.1029
328.0996
328.0951
327.0918
327.0873
326.0839
326.0795
325.0761
324.0682
323.0605
316.0994
315.0916
314.0964
314.0838
305.1073
304.1121
304.0994
304.0950
303.1042
303.0998
303.0917
302.0964
302.0921
302.0839
301.0886
301.0842
301.0761
300.0888
300.0808
300.0764
300.0683
299.0730
Rel. Magnitude (%)
3.5
28.1
1.6
100.0
13.5
1.3
57.4
16.7
67.3
6.3
26.4
6.5
26.0
3.0
11.9
1.4
5.3
3.3
1.1
1.7
1.7
1.0
1.0
1.9
1.7
1.3
1.1
3.6
2.1
4.6
7.8
3.7
3.3
14.2
1.4
2.4
1.1
5.4
2.5
1.8
10.3
Elemental Composition
[13C2C22H15N2]+
[13CC23H15N2]+
[13C2C22H14N2]+
[C24H15N2]+
[13CC23H14N2]+
[13C2C22H13N2]+
[C24H14N2]+
[13CC23H13N2]+
[C24H13N2]+
[13CC23H12N2]+
[C24H12N2]+
[13CC23H11N2]+
[C24H11N2]+
[13CC23H10N2]+
[C24H10N2]+
[13CC23H9N2]+
[C24H9N2]+
[C24H8N2]+
[C24H7N2]+
[C23H12N2]+
[C23H11N2]+
[C24H12N]+
[C23H10N2]+
[C22H13N2]+
[C23H14N]+
[C22H12N2]+
[13CC21H11N2]+
[C23H13N]+
[13CC22H12N]+
[C22H11N2]+
[C23H12N]+
[13CC22H11N]+
[C22H10N2]+
[C23H11N]+
[13CC22H10N]+
[C22H9N2]+
[13CC23H11]+
[C23H10N]+
[13CC22H9N]+
[C22H8N2]+
[C23H9N]+
2
Mass Error, (ppm)
0.2
0.0
-0.1
0.0
0.3
0.4
0.5
0.3
0.2
0.2
0.2
0.3
0.4
0.3
0.3
0.3
0.1
0.1
0.3
-0.3
-0.1
-0.1
-0.3
-0.1
-0.1
-0.3
-0.1
-0.3
0.0
-0.1
0.0
0.3
0.1
0.0
0.2
0.3
-0.2
0.1
0.3
0.2
0.2
299.0685
298.0652
297.0574
296.0495
288.0808
278.0964
277.0886
276.0807
275.0730
274.0777
274.0651
273.0573
272.0621
270.0463
1.5
3.4
3.7
1.3
1.4
1.8
2.7
1.6
3.9
2.8
1.6
2.4
2.2
1.3
[13CC22H8N]+
[C23H8N]+
[C23H7N]+
[C23H6N]+
[C22H10N]+
[C21H12N]+
[C21H11N]+
[C21H10N]+
[C21H9N]+
[C22H10]+
[C21H8N]+
[C21H7N]+
[C22H8]+
[C22H6]+
3
0.1
0.2
0.3
0.1
0.0
-0.2
-0.2
-0.3
0.0
0.0
0.1
0.0
0.0
-0.4
Figure S1. Schematic diagram of a 7-section open cylindrical cell. Dimensions of segments are in
millimeters. The angular extent of each detection and excitation electrode is 120º and 60 º for
optimal detection.
Figure S2. The instrument set-up for charge reversal experiments induced by electron ionization
(top) and UV irradiation (bottom).
Figure S3. Potential energy profiles for a negative ion (bottom) and the positive ion (top) formed
by essentially vertical (i.e., Franck-Condon) excitation. Because the positive product ion is formed
in an excited state, it may readily fragment (see text).
Figure S4. Trajectory of a cyclotron-excited ion before (blue) and immediately after (red) charge
reversal, as a result of collision with a gas molecule.
The post-excitation radius determines
precursor ion Ekin and its Eint after collision (see text).
Moreover, the precursor negative ion
maximum post-excitation radius is clearly 1/3 of the cell radius.
4