MICROWAVE SPECTRA OF
FLUORO FORMYLOXYL
AND
FLUORO SULFATE
RADICALS
Štěpán Urban, Juraj Varga, Lucie Kolesniková,
Zuzana Meltzerová, Tereza Uhlíková,
Jan Koucký, Patrik Kania,
Hans Beckers, and Helge Willner
HELMUT BECKERS AND HELGE WILNER
Bergische Universität Wuppertal
FB9, Anorganische Chemie
Gaussstrase 2O
42097 Wuppertal, Germany
Task in this paper: Preparation of radical precursors
ŠTĚPÁN URBAN, JURAJ VARGA, LUCIE KOLESNIKOVÁ,
ZUZANA MELTZEROVÁ, TEREZA UHLÍKOVÁ, JAN
KOUCKÝ, PATRIK KANIA
Institute of Chemical Technology, Prague
Laboratory of Highl Resolution Molecular Spectroscopy
Technická 5, 16628 Prague 6,
Czech Republic
In this paper:
Spectroscopy (experiment, theory, assignments, analysis)
RADICAL SETUP
RADICALS STUDIED:
Fluoro formyloxyl and fluoro sulfate radicals
Both the radicals are of an atmospheric interest
(eg. FCO2 can be produced by a stratospheric
degradation of HCF’s ). Their atmospheric
abundance can be now enhanced because of

massive eruptions of the Eyjafjallajokull
volcano containing Fluor and Sulfur.
FCO2 FLUORO FORMYLOXYL RADICAL
Pyrolytic preparation from special precursor
a ≡ C2
F C O ←570K→ FC0 ● + FC0 ●
2 2 4
2
2
σ
b
Molecular symmetry C2v,
asymmetric top
N, Ka, Kc, J, F
c
FRAGMENT OF FCO2 SPECTRA
RADICAL FCO2• − MOLECULULAR PARAMETERS (MHZ)
 Praha + Lille 130 − 380 GHz
 217+202=419 Transitions
constant
value [MHz]
εaa
−83.337(81)
εbb
−794.582 (59)
εcc
−44.1739 (69)
13 752.225 95 (172)
ΔSN
4.046(100) · 10−3
B
11 310.318 52 (115)
ΔSKN
−19.78 (44) · 10−3
C
6 192.799 068(185)
ΔSK
15.60 (51) · 10−3
δSN
1.980 (51) · 10−3
δSK
−3.017 (182) · 10−3
A
ΔN
ΔNK
ΔK
δN
δK
7.8167 (43) · 10−3
−0.2899 (184) · 10−3
15.5231 (186) ·
10−3
3.37614(215) ·
10−3
10.7461 (49) ·
10−3
aF
1.5 Taa
−85.821(199)
¼(Tbb − Tcc)
39.924 (37)
½(Cbb+ Ccc)
0.01078 (213)
s
Kolesnikova, et al, J. Chem. Phys, 2008
−78.27 (77)
0.03
RADICAL FSO3•
(First time study!!!)
Quantum chemistry predicts:
•
•
Rotational constant B  5 GHz
The GS structure WAS not quite sure > there
were 3 possibilities:
1. Asymetric top (no excluded states)
2. Symmetric top in A2 electronic state 
allowed only states with K=0,3,6, 9,…..
3. Symmetric top in E electronic state 
allowed only states with K=1,2,4, 5,…..
Preparation by pyrolysis:
F2S2O6 ←440K→ FS03● + FS03●
RADICAL FSO3• (The first scan over 10 GHz,
more than 850 unknown lines have been observed )
Without mg. f.
With mg. field
Without mg. f.
With mg. field
ZEEMAN EFFECT
.
Frequency /2N
Frequency /2N
21
21
RADICAL FSO3•
N'
N' 20
18
15
12 9 6 3 0
20
K
19
03 6 9
12
15
18
19
5190
5190.1
5190.2
5190.3
5190.4
5190.5
5190.6
5190.7
5190.8
5190.9
5191
5194
5194.2
5194.4
5194.6
5194.8
B eff [MHz]
5195
5195.2
5195.4
5195.6
5195.8
5196
B eff [MHz]
-4
-4
3,0x10
2,5x10
-4
2,0x10
-4
-4
1,5x10
intenzita [a.u.]
intenzita [a.u.]
2,0x10
-4
1,0x10
0,0
-4
1,0x10
-5
5,0x10
0,0
-5
-5,0x10
-4
-4
-1,0x10
-1,0x10
207610
207615
207620
207625
frekvence [MHz]
N″ = your
19 footer
J″ = 19,5
Here comes
Page 15
207630
207635
207770
207780
207790
207800
207810
frekvence [MHz]
N″ = 19 J″ = 18,5
207820
207830
207840
FINE SPLITTING - RADICAL FSO3
•
RADICAL FSO3: A1 – A2 SPLITTING OF K=3 TRANSITIONS
HSPLIT = ε[(J+3 + J-3), Jz]+ +
+ εJ J2[(J+3 + J-3), Jz]+ + εK [(J+3 + J-3), Jz3]+ +
+ h (J+6 + J-6) +
+ hJ J2(J+6 + J-6) + hK [(J+6 + J-6), Jz2]+
Matrix elements of the red and black operators are strongly
mutually correlated and there is a possible contact
transformation of the black operators to the form of the red
ones and the opposite contact transformation
Rotational and centrifugal distortion paramaters (MHz)
Parameter
A-reduction
B-reduction
A
252.372*
252.372*
B
5195.52804 (22)
5195.52929 (36)
3.76185( 44)
3.7668 (10)
DNK × 103
–1.27938 (99)
–1.2864 (24)
√2 ε × 103
–
1.797 (13)
εN × 106
–
0.0386 (57)
εK × 106
–
–1.30 (10)
HN × 106
– 0.00816 (34)
0.0116 (14)
HNK × 106
0.1954 (10)
0.0711 (45)
HKN × 106
– 0.3553 (19)
– 0.1661 (72)
DN × 103
h3 × 109
h3N × 1012
LN × 109
– 6.35 (10)
–
– 0.243(43)
–
0.000776 (85)
– 0.00300 (83)
– 0.00660 (33)
– 0.0582 (51)
LNK × 109
0.01260 (77)
0.289 (21)
LKKN × 109
– 0.0088(13)
– 0.389 (26)
LNNK × 109
Fine splitting paramaters (MHz)
Parameter
eaa
ebb
A-reduction
B-reduction
–37.507 (30)
–135.9719 (80)
– 0.9828(43)
–37.484 (29)
–135.9671 (77)
– 0.09928 (41)
(DSNK + DSKN) × 103
2.894 (67)
3.097 (65)
DSK × 103
–2.387(77)
0.074
–2.202 (76)
0.071
DSN × 103

RADICAL FSO3: A1 – A2 SPLITTING OF K=3 TRANSITIONS
HSPLIT = +ε[(J+3 + J-3), Jz]+ +
+
εS [(J+
3+
3
J- ),
S z]+
+ εJ J2[(J+3 + J-3), Jz]+ + εK [(J+3 + J-3), Jz3]+ +
+ h (J+6 + J-6) +
+ hJ J2(J+6 + J-6) + hK [(J+6 + J-6), Jz2]+
SOME ADDITIONAL STUDIES OF THESE
RADICALS ARE IN PROGRESS
Fluoro formyloxyl radical
Isotopologues with 18O
Rotational spectra in excited vibrational states
Detailed molecular geometry
Fluoro sulfate radical
Isotopologues with 18O
Qualified improvement of our estimation of A r. c.
?? Forbidden transitions >>molecular geometry
?? Pseudo JT effect >> Rotational spectra in excited
vibrational states