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30.4-nm He(II) Photoelectron spectra of organic molecules
Journal of Electron Spectroscopy and Related Phenomena, 23 (1981) 281-322 Elsevler Sclentlfic Pubhshmg Company, Amsterdam - Prmted In The Netherlands
Data bank
30.4-1~1 He(II) PHOTOELECTRON MOLECULES Part IV. Fluoro-compounds
SPECTRA OF ORGANIC
(C, H, F)*
GERHARD BIERI? Physrkahsch-Chemrsches Instztut der Unwersrtat Base& Klmgelbergstrasse 80, CH-4056 Base1 (Swrtzerland} LEIF ASBRINK The Royal Institute of Technology, Physrcs Department, S-100 44 Stockholm (Sweden)
70
WOLFGANG VON NIESSEN Instltut fur Phyakahsche Chemle, Technrsche Universltat Braunschwerg, Hans-SommerStrasse 10, D-3300 Braunschwelg (W Germany) (Received
5 January 1981)
REMARKS
Part IV of this Data bank IS concerned ~th the He(I1) photoelectron spectra of 30 fluoro-compounds, mcludmg all fluoro-denvatlves of methane, acetylene, ethylene and benzene, The assignment of the observed bands 1s obtamed from semlemplrlcal HAM/3 calculations [2 1, from many-body Green’s function calculations [3] combmed urlth Tamm-Dancoff Green’s functron calculations [4] for the mner valence regon, and/or from other types of calculations published previously The calculations are complied m the Tables together ~th the expenmental lomsatlon energes The 30 4-nm He(H) photoelectron spectra axe shown m the followmg Figures (abscissa scale m eV, ordmate gwes count-rate m arbitrary units For other delis, see Part I**) The spectra of closely related molecules are presented together on one page The ordermg according the sum formula has therefore not stnctly been followed * For Part III, see ref 1 *i Present address The Royal Institute of Technology, Stockholm, d Electron Spectrosc Relat Phenom , 20 (1980) 149 0368.2048/81/0000-0000/$02
50 o 1981
Ekevler Sclentlflc
Sweden
Pubhshmg Company
282
He
CF 4
CHF,
283
r,
I,
I
25
I
I
I,
20
15
10
F-C’=C-F
25
20
15
10
H-CC-F
+++,
25
20
15
10
285
F
F
I
(filtered spect rum) b
20
25
30
F
10
15
F \ F
11
11
25
‘1
’
1
20
”
‘1
I
15
’
“‘I”
10
286
F
F
-I /-
15
10
15
10
F
F
25
20
287
25
F /
288
,
I
I,,
25
I,
1
I,
20
CF,-CEC-H
I,,
,
15
,
,
,
1
,
10
289
F-CzC-CsC-F
CF3-CX-CX-F
I
25
290
F
F F
0
F
0
25
F
20
15
10
F F F ti
I
11
III
25
F 0
F
1,
I1
20
I1
11
15
1
f
II
I
10
I
291
25 F
0 0
F
F
F
:I
292
F F
1,
I
25
I
Ex F
F
I
I
(
20
11
1
’
(
15
I”’
1’1
10
7
293
25
15
20 F
v 0
F
F
i
I
d
4
v
:
294
F
25
II
(
25
15
20
I
I
I7
11
20
1
11
11
15
10
1
c
“I’
10
295
F
0 0
F
F
0 0
HF
25
I
I
I
,
25
20
I,
,
I,
15
1
20
,
(
,
15
10
297
EXPERIMENTAL
Samples CF,, C2 F, , C2 F4, CZ HF, C4 F, and C5 F, were obtamed from electrical discharges m vapours of a smtable substrate, as outlined m ref 5. The samples were purified by bulb-to-bulb &stfilatlon, momtored by He(I) spectroscopy. CH2 Fz and CZH5 F were syntheslsed accordmg to the method outlmed m ref 6 HF was obtamed from heated KHF, salt and F, was prepared from electrolysis of molten KHF, [ 71 1,2,3-Trlfluorobenzene was kmdly supplied by Dr J P Maler and Mr P Forster (University of Basel) All other samples were of commercial origm Spectra The spectrum of tetrafluoroethylene was obtamed by usmg filtered He(I1) radiation A thm polystyrene film was placed between the light source and the lomsation chamber. The 58.4-nm hne of the He(I) rachatlon was reduced by a factor of 104, whereas for He(I1) ra&atlon a transmlsslon of -10% was obtamed
TABLES
Stu te speczfzca tzon, orbs tul no ta tzon r-type charactensed by =cc TF
orbltals are supplementarily
acetylemc, ethylemc or benzemc r-orbital out-of-plane fluorme lone-pm orbital
+ or - speclfles the sign of the correspondmg hnear combmatlon for molecules with Dmh , CZh or CZV symmetry (except fluorobenzenes) An additional guide for the speclflcatlon of the electronic states 1s gwen by the valence orbital number J, which 1s mtroduced for large molecules (C, Fq, C6 Fe, Cd%, GA F4 and G Hs F3 ) Ionzsatzon energzes and uzbratzonal frequenczes For overlappmg bandsystems which cannot unambiguously be assigned, the band area 1s Dven This 1s mdlcated by open parentheses The observed vibrational progressions m the photoelectron spectra of the fluorobenzenes are not included m the Table A vlbromc analysis IS more accurately obtamed from ion-emlsslon spectra For a summary, see ref 8 References The references m the footnotes below each section of the Table are complied m the Supplementary References (alphabetical by author), pp 319-321
298
VALENCE IONISATION ENERGIES (eV) AND OBSERVED VIBRATIONAL GRESSIONS (cm-’ )
Carbon tetrufluorde + W-l
2
PRO-
CF4 (Td ) HAM/3
U(SCF)’
Exp
It1
16 46
16 50
16 2
ii 4t2 ii le
17 26 18 16
(17 51)b 20 60
17 4 18 5
2; 3t2
2166
24 00
fi 4a1
24 71
27 26
2t2
4100
301
44 54
810e
(18 30)ae
400 645e
43 87c
22 1 (217O)k” 25 1 (25 12)d 40 3f
49 50
43 Bf
730=
*Ref 54, symmetry-unrestricted (C,) ab mltlo Hartree-Fock calculation bNot converged c a’ symmetry, a” at 44 87 eV dAdlabatlc lomsatron energies eRef 19, He(I)/He (II) fRef 5, MgK(Y,YM{ radlatlon Further references He(I), refs 22, 45, 62, 74, He(I) angular dlstnbutlon, ref 23, He (I)/He(II), ref 51, photoelectron-photolon comcldence, refs 16, 60, 71, Mg Kcwradlat&on,ref 70, Al Karradlatlon, ref 37, electron energy-loss spectroscopy, ref 42 Fluoroforrn
CHFJ (C,,)
G w’
HAM/3
MS-X(&*
g 6a1 ii la2 ii 5e
14 94 15 71 16 16
15 56 17 41
2; 4e
17 00
17 10 18 68
G 3e
20 47
2141
i!Z Sal F” 441
20 81 24 70
20 08 23 93
2e 3ul
39 78 42 22
36 56 38 80
Exp 14 8 15 5 16 2 17 2 (17 o@c 20 7
1030c 570 480
(20 oo)b*c 20 7 4e 42)bC 15f 0’
24 (24 39 42
2660d 1050
aRef 4 bAdlabatlc lomsatlon energies =Ref 74 dThls work =Due to mcreased pressure, no He peak at 24 6 eV was found m this experrment ‘Ref 5, Mg Ka, Y MS radlatlon Further references He(I), ref 62, He(I) angular dlstnbutton, ref 23, He(I)/He(II), ref 19, electron energy-loss spectroscopy, ref 42
299 MethyZene fluonde
CH2 F2 (C,,)
5
HAM/3
MS-Xc?
FOCI + Qb
13 06
14 18
13 31
(VP
a% 2b,
EXP 13 3
1120d
(12 74)c’d ii
15 05
154
15 67
1697 16 11
15 38
154
1576
1763
15 83
4b2
15 46
B 6a, E la2
15 8 (15 58)c*d 19 1
19 22
18 72
18 05
i% 3b2 F 5aJ
19 17 19 33
19 69 18 77
18 90 18 79
G 4q
24 05
22 89
24 0
38 45 39 95
36 33 37 28
38 2’ 40 If
980d 480 680d
(18 31)=
2b2 3a1
19 1 19 1
aRef 4, compare aiso ref 6 bRef 49, frozen-orbhal CI + quadruples corrections CAdlabatlc lomsatlon energies dRef 74, He(I) eRef 62, IE, = 18 17 eV f Ref 5, Mg KCU, Y k?{ radiation Further references He(I)/He(II), ref 19, He(I) angular dwtnbutlon, ref 23, electron energy-loss spectroscopy, ref 42 Me thy2 fluonde
CH, F ( C!J”)
G OP-’
HAM/3
MS-Xcta
GFb
if
2e
13 16
13 96
13 39
(0 94)
z
5q
18 23
17 60
16 88
g lf?(aF) E 4a,
17 50 23 48
18 77 2186
17 19 23 82’ 28 65
(0 93) (0 92) (0 84)
301
38 26
37 70
EXP 13 1 (12 54)d’”
1290e 880 695
17 0 17 0 23 4
(0 021)
34 53
(0 030)
36 87’
(0 032)
37 80 37 81
(0 11) (0 046)
38 23 38 66 40 58
(0 16) (0 31) (0 03i)
42 38 42 75
(0 083) (0 035)
38 4’
aRef 4 bBasls set (9sSp/4s), relative mten&es qven m parentheses ’ 2ph-Tamm-Dancoff Green’s fun&on results, the (e)-’ states are calculated to be non-&agonal (2e)-’ = 13 00 eV (0 037,O 89), (Is)-’ = 17 10 eV (0 87, 0 042) dAdlabatlc Jon&&Jon energy eRef 46 fRef 5, Mg K&, Y MS radlatlon Further references He(I), ref 62, He(I)/He(II), ref 19, He(I) angular dlstnbutlon, ref 23, electron energy-loss spectroscopy, ref 42
300 Difluoroace ty lene C2 F2 ( Dmh)
* w
HAM/3
2
11 a2
2% (ncc)
STO-3G
GFa
8 49
1131
EXP 1160 (11 18)@
2420f 825
(11 49)e .i
lTr, (RF_)
B 1% E 50s 5
(nF+)
40,
B 40,
17 11
1598
18 14
17 7
17 74
1709
18 62
18 5
19 93
17 87
20 74
20 6
2199
19 33
20 57b
(0 55)
217
26 62
2120 25 05b
(0 33) (0 095)
25
26 13
3%
40 84
3%
4143
43 15
43 19
25 72
(0 44)
27 48
(0 23)
30 60
(0 11)
40 94b
(0 45)
42 17 42 47
(0 16) (0 062)
40 6gb
(0 20)
4185 43 37
(0 33) (0 083)
&Bas= set (9s5pld) bTamm-Dancoff Green’s function results, relative mtenshes given m parentheses CAdlabatlc lomsahon energy dRef 10, He(I) eMost mtense peak of VIbratlonal progresslon f Ref 11, He( II)
Tefrafluoroethylene
C2F4 (DZh)
G (FT’
HAM/3
STO-3G
GFa
x
10 71
7 50
1110
f&u (‘kc)
EXP 10 69 (10 14)c*d
1690f 740
(10 56)e
A 4b3,
16 06
13 65
16 62
159
6a, i? 4bzU
16 25
12 72
16 75
16 6
16 22
13 63
17 04
16 6
5
16 34
14 24
17 27
166
16 41
14 32
17 42
16 6
17 31
15 10
18 12
g
k(nF)
17 6
740f
(17 51)&d
G lbzg (nF) H 3b3,
17 68
16 25
18 87
19 71
16 31
19 74
18 2 19 4 (19 19)Sd
7
lb,
3bzU ii: 5ag
2
('llF)
19 36
18 26
20 14
194
20 25
18 56
2130
210
20 50
19 19
2184
210
660’
301 Tetrafluoroethylene
C2F4 (DZk)
(contrnued)
w-’
HAM/3
STO-3G
GFa
L 4blu
22 54
20 53
22 51b
(0 35)
22 74
(0 28)
23 40
(0 25)
27 94b
(0 53)
29 78 3157
(0 13) (0 084)
42 46b
(0 065)
42 68
(0 51)
43 59 42 70b
(0 05) (0 091)
43 11
(0 55)
43 49
(0 05) (0 083)
s
ii!? 40,
2hs
262,
3bl,
3nl?
27 35
26 63
4154
40 08
41 a4
39 99
43 22
40 96
42 10
43 70
44 24b
EXP
44 45
(0 13)
44 64
(0 13)
44 67
(0 08)
44 71
(0 062)
44 94
(0 07)
45 45 44 3gb
(0 05) (0 068)
44 71
(0 058)
44 78 44 91
(0 13) (0 063)
45 23
(0 14)
45 64
(0 097)
22 5
26 3
'Basis set
(9s5p) b Tamm-Dancoff Green’s function results, relative mtensltles pven m eMost intense peak of parentheses CAdlabatlc lomsatlon eneraes dRef 20, He(I)/He(II) vlbrahonal progresslon f Ref 48, He(I) Further references, He(I) angular dlstnbutlon, refs 68, 69, CNDO/SS, ref 33, resonance electron capture, ref 24
Fluoroacetylene
CzHF
(CL,)
+ w’
HAM/3
2 2n(7kc)
1168
STO-3G
GFa
9 00
1134
EXP 11 50 (11 26)c’d
ii
70
la 28
17 23
18 12
la 0
ii
Ia
17 56
16 68
18 31
18 0
?
60
21 23
19 33
2114
212
5
50
25 11
26 28
24 85b
(0 47)
26 52
(0 15)
29 67
(0 24)
24 3
21aod 1210
302 Fluoroacetylene
CzHF
@ (d-’ 4a
(G,)
(contmued)
HAM/3
STO-3G
GFa
4125
43 25
40 8gb
(0 17)
42 04
(0 28)
EXP
42 79
(0 12)
43 40
(0 11)
aBaw set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles gwen m parentheses CAdlabatlc lomsatlon energy dRefs 41,43, He(I) Trffluoroethylene
C2HF3 (C,)
+ (P)--’
HAM/3
2 40” @cc)
10 48
STO-3G 7 85
GFa
EXP 10 62
10 81
(10 14)c’d (10 54)e 14 86 15 62 16 01
12 24
16 58 16 57 18 26
14 01 14 81
E la” (77~) ii 12a’
18 52
7
2 16a’ Z 15a’ E 3a” (RF) ii 14a’ i% 2a” (71~) F 13a’
lla’
3 104’ i7 9a’ 8a’ 7a’ 60’
13 34 14 02
14 7 16 0
1502 16 42
-16
16 94
5
16 8 16 8
1534
17 08 17 36 18 26
1723
19 22
19 44
17 61
20 28
18 7 20 1
19 75
la 77
20 54
2193 25 95
20 57 27 13
23 06b 27 34b
(0 37) (0 09)
28 60
(0 46)
39 24
4126 4161 43 13
39 56 4121
18 0
20 1 219 25 8
aBasls set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensitles given m parentheses CAdlabatlc lonlsatlon energy dRefs 68, 69, He(I) angular dlstrlbutton eMost intense peak of vlbratlonal progression Further references resonance electron capture, ref 24 l,l-DQ’luoroethylene
CzHzF2
(C,,)
HAM/3
STO-3G
2 261 (mcc)
10 59
ii 5b2
14 83
+
w-’
GFa
EXP
8 25
10 77
13 25
15 33
10 (10 (10 14 (14
70 29)c’d 69)e 9 06)Cf
1600’ 720 1180’
303 1,l -D$luoroethybne
CzH2 F2 (C,,)
(continued)
+
w’
HAM/3
STO-3G
GFa
5
8U' 4bz
15 80
13 10
15 81
15 8
16 00
16 07 16 52 18 49
16 1 16 1 18 2 19 7
E
b 102 (BF-) Z 7al
16 03 18 25
14 31 13 90 17 47
F 161 (nF+) i? 3b2
18 20 19 60
16 96 17 83
18 71 19 89
fi 6al ‘i 5q
2153 25 41
20 41 27 07
21 83b 25 93b 27 29 29 86 30 80
262
39 37
4130
41 52b 4182 4187 4196 42 20 42 31 42 54
43 22
4al
43 67b 43 92 44 22 44 43 44 66
EXP
18 2
(0 37) (0 21) (0 45)
21 5 25 2
(0 05) (0 (0 (0 (0 (0 (0
06) 04) 20) 12) 077) 073)
(0 071) (0 11) (0 37) (0 085) (0 069) (0 096) (0 063)
abash set (9s5p/4s) bTamm-Dancoff Green’s function results, relatwe mtensltles given m parentheses CAdlabatlc lomsatlon energres dRefs 68, 69, He(I) angular dlstrlbutlon eMost intense peak of vIbrational progression ‘Ref 48, He(I) Further references He(I), ref 74, photolomsatlon, ref 64, resonance electron capture, ref 24 as-1,2-Dzfluoroethylene 3
(VP
2 2ht @cc)
C2H2 Fz (C,,)
HAM/3
STO-3G
10 25
7 81
GFa
EXP
10 54
10 62 (10 22)=-d
1600df 1330
(10 63)e
1030 250
AT 7aj
13 97
1171
14 30
ii 6b2
15 28
13 02
15 16
14 0 1430d (13 79)CA 1020 240 14 9 (14 89)Gd
304 cls-I,P-LWluoroethylene G w-l
C$N, Fz (C,,)
(contmued)
HAM/3
STO-3G
GFa
16 12
16 64
16 2
17 28
14 33 15 01
17 20
17 1
17 04
15 66
17 41
17 1
18 32 18 72
16 36 18 44
18 84 19 34
18 8 18 8
21 28
20 39
21 OBb 2140 26 06b
25 28
26 76
27 33 39 15
3bz
4131
30 06 41 03b 4115 4161 4163 42 03
39 55
34
4167
42 18 41 73b 42 03 42 15 42 37
EXP
(0 70)
20 9
(0 15) (0 37)
25 2
(0 (0 (0 (0
31) 054) 075) 052)
(0 063) (0 17) (0 18) (0 083) (9 16) (0 057) (0 15) (0 24)
aBas~ set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles given m parentheses ‘Adlabatlc lonwatlon energies dRef 52, Ne(I)/lon-emwon eMost intense peak of vlbratlonal progression f f 10 cm-’ Further references He(I) angular dlstrrbutlon, refs 68, 69, synchrotron radiation, ref 44, photoelectron-photoloon comcldence, ref 72, resonance electron capture, ref 24 trans-1, P-Dzfluoroe thylene CZHz F2 (C&h) 5
w-’
HAM/3
2
2% @cc)
10 11
STO-3G 7 82
GFa 10 57
EXP 10 63
1650d
(10 21)C*d 1280 ii 7a,
13 79
1182
14 28
ii 6b,
15 11
13 03
15 39
16 17 17 18 18
14 14 15 17 17
1668 1703 17 37 19 00 19 10
e 5 2 Z G
lb, (RF-) 6a, 1% 5ag 5b,
(nF+)
14 41 09 41 63
19 30 50 64 07
(10 14 (13 15 (15 16 17 17 18 18
61)e 0 51)C.d 1 09)C’d 3 0 0 8 8
530 530d
305 trans-l,Z-Dlfluoroethylene
CZHz F,
(C,,)
(contrnued)
G w
HAM/3
STO-3G
GFa
i7
2137
20 89
20 81b
(0 12)
2109
(0 17)
2148
(0 54) (0 088)
48,
‘i: 4as
3bu
25 06
38 68
26 59
4123
25 3gb 25 83
(0 078)
26 00 26 37
(0 11) (0 27)
27 41 29 90
(0 18) (0 091)
41 23b 4124
(0 064) (0 082)
4155
(0 085) (0 063) (0 095)
4173 4181
3%
39 25
4140
EXP
4186 42 32 41 44b 4153 4194 42 12 42 15 42 81
(0 (0 (0 (0
20 9
25 2
05) 17) 093) 069)
(0 05) (0 24) (0 20) (0 056)
abash set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles gwen m parentheses CAdlabatlc lomsatlon energies dRef 52, Ne(1) eMost Intense peak of vibrational progresslon Further references, He(I) angular dlstrlbutlon, refs 68, 69, synchrotron radlatlon, ref 44, photoelectron-photolon comcldence, ref 72, resonance electron capture, ref 24 Vznylfluonde
CZH3 F (C,) HAM/3
STO-3G
10 34
10a’
ii 9a’
+
(VP
.% 2a” (act )
ii E 5 E 8
la” (KF) 8a’ 70’ 6~’
GF*
EXP
8 30
10 43
10 63 (10 36)c’d
1530f 1330
(10 55)e
510
14 19
12 13
14 02
13 8
14 44
13 30
14 51
16 17 18 20
14 15 17 20
16 16 18 20 20
14 16 16 17 20
79 13 34 86
79 87 22 52
51 81 13 46b 96
(0 66) (0 18)
5 7 7 9 2
Vanylfluonde CzH3 F (C,) *
NJ)-’
3 5n’
(contmued)
HAM/3
STG-3G
24 76
26 60
GFa 24 34b
(0 053)
24 87
(0 040)
26 12
(0 50) (0 043)
26 26 4a’
39 66
4122
EXP
29 30
(0 081)
40 68b 4121
(0 072) (0 044)
4170
(0 042)
4172 4189
(0 053)
24 5
(0 25)
‘Bask set (Q&p/48) bTamm-Dancoff Green’s function results, relative mtensltles @ven m parentheses CAdlabatlc lonlsatlon energy dRefs 68, 69, He(I) angular dlstrlbutlon =Most intense p@ak of nbratlonal progrestuon ‘Ref 48, He(I) Further references He(I), refs 63, 74, photolonrsatlon, ref 64, photoelectron-photoion comcldence, ref 30, resonance electron capture, ref 24 Efhylfluorzde
C2 H5 F (C,)
+
(y7)-1
HAM/3
x
30”
12 12 12 61 14 07
12 4 12 9 14 0
E 2a” fi 80’ E lo”
14 11 16 01
14 5 16 0
F 7a’
17 60
a 6u’
2103
ii 1Oa’ E 9a’
ii
6cl’
24 33 37 38
17 1 210 (20 85)W 24 6
“Adlabatlc lonlsatlon energy b Ref 66 ‘This work Further references He(I), ref 76 3,3,3-l’kfiuoropropyne
CJ HF3 (G,)
5
w-’
HAM/3
EXP
2
6e @CC)
1166
12 (11 15 15
z la* ii 1Oq
15 27 15 37
1130b
17 1
17 33
4o’
EXP
1 96)“.b 3 3
1250’ 525
307
3,3,3-Trzfluompropyne +
C3 HF3
((23,) (contmued)
HAM/3
(P)-’
EXP
2; 5e
15 81
6
16 70
17 1
E 9a,
1804
184
F 3e
20 21
i? aa1
20 49
4e
ii
?a1
22 92
‘i
6q
25 72
2e
39 39
501
42 34
aAdlabahc
lomsatlon
lhfluorodmetylene
energy
15 9
20 6 -212 23 9 -25
bRef
8
9
C4 F2 (D_+,)
*
(VP
HAM/3
STO-3G
2
277,ehx-1
10 50
7 72
GFa
EXP
10 36
10 35 (10 05)“,d (10 33)=
2320& 1550 520 300
2
27L (Qc+)
12 71
1136
13 14
129 (12 sa,=*d
2290h 1450 520
4%
16 63
16 84
18 20
17 9
16 68
16 98
18 25
18 1
18 23
1792
19 76
19 3
19 64
18 91
20 87
2117
20 76
20 75b
(0 58)
23 99
26 11
2157 26 4ab
(0 53)
26 45
27 85
27 19 27 10b
40 26
43 56
28 10 42 21b
(0 08)
42 67
(0 10)
42 74
(0 35)
43 15
(0 15)
43 37 42 77b
(0 08)
42 83
(0 25)
43 57
(0 10)
40 28
43 56
20 7 216
(0 29) -24
3
(0 16) (0 13) (0 64)
(0 39)
abash set (9s5p) bTamm-Dancoff Green’s function results, relatwe mtenshes qven m parentheses =Adlabatx lonlaatlon energies dRef 10, He(I) =Most mtense peak of VP bratlonal progressIon f Ref 3, lonemuwon gflOcm_’ hRef 1 I
308 Perfluoropentadlyne-I,3
C5 F4 (CJ,)
J
G w’
HAM/3
EXP
2324
2
10 64
10 85 (10 58)&b
8e (rcc)
2280b” 1440 1140 880 710
21,22
A 7e (ncc)
12 77
20
ii la2
14 69
15 2
19
i? 16a1
15 2
17,18 15,16 13,14
5 6e j? 5e F 4e
15 04 15 24 16 11
12
G 15al
11
i;i 14q
9,lO ? 8 J
13 3 (13 09)Gb
15 17 18 19
16 35 18 17 19 50
3e (71~) 13q
340 1160b 760 340c
8 1 3 6
20 5
19 65 20 61
210 218
7
ii 12Ql
22 59
238
6 5
z
llq lOa,
24 64 26 52
25 2
3,4
2e
38 79
2
901
1
801
39 94 4175
aAdlabatlc lomsatlon energies bRef 3, lon-emlsslon c+1O cm-’ Further references He(I), ref 10 Hexafluorobenzene
Cd F6 (Deb ) HAM/3
--e (SCF)a
3233 X 2elg (ACC)
10 68
12 35
31
x
12 30
15 92
30
ii 2bzu
13 72
16 70
28,29
C 6e2g
14 74
17 70
27
5
1561 1581
19 20 19 41
1588 16 16
19 66 19 88
J
25,26 24 22,23
Q w-l
2%
(%x)h
lazs 6el, 1bZs
(TF)
le2”
@F)
EXP s
10 2 (9 906)12 8 (12 577)b” 140 (13 847)‘*’ 14 8 (14 760)b” 15 9 (16 2e
1516’ 1492c 1420’ 428
309
Hexafluorobenzene I
9
C6F6
(&h)
(d-l
(contrnued)
HAM/3
--E (SCF)a
Exp
17 23 18 18
20 74 20 83
17 6 (18 If
20,21
lelg
18,19
5e2s
17
%u
18 21
2189
15,16
5el,
18 48
2105
I 19 0)
14
5a1g
19 18
22 65
20 3
13
lb?,
19 39
12 10,ll
4blu
24 30(‘) 2187
20 3 20 3
4e2g
20 10 2145
4el,
25 32
26 31 3107
25 6
35 28
@F)
@F)
859 7
4a1,
29 04
6
3blu
38 98
495
3e2,
39 19
2,3
3eh
39 75
1
3alg
40 15
22 4
aRef 58, mmlmal-basis-set “ab mltlo” calculation bAdlabatlc lomsatlon energies ‘This work, high-resolution He(I) spectrum dIE, (2elJ1 = 9 90 eV, ref 73, He(I), IE, (2e,,)-’ = 9 91 eV, ref 69, He(I) angular dlstrlbutlon eBand-maxlmum at 16 5 eV fBand-maxlmum at 18 6 eV sRef 29, lon-enusslon, see also ref 12, laser-Induced fluorescence hOften referred at the g state (e g , refs 1,2, 32) Further references He(I), refs 7, 21, 33, 55, 74, He(II), refs 21,59, 61, Ion-emwon, refs 1, 2, 28, laser-Induced fluorescence, ref 12, in sohd matrix, ref 13, photolrphotoIon comcldence, refs 32, 35, resonance electron capture, ref 36, He(I) angular d&nbutlon, ref 47 Pentafluorobenzene
C6HF5
(C,,) HAM/3
I
+ w-’
30
if
29
2
28
E 4bl (GX)
12 21
27
E
13 57
26
5
3a2
(Tcc)
5bl hx)
13b2
10 29 10 61
Exp 99
(9 64)qb -10 1 12 7 (12 5o)“.b 13 9 (13 71y
25 24 23 22 21 20
14 16
20al i% 12b2
14 71
llbz 19a1 3bl
15 44 cnF)
2a2 tnF)
18al
15 15 15 16
58 74 91 32
P) 14 9 (14 79)qb (15 7d
e
310 Pentafluorobenzene 1
*
19 18 17 16 15
C6HF5
(confmued)
w-’
HAM/3
2bl (TF) la2 (AF) lob2
16 52 16 93 17 31
lb1
(773)
17q
14 13
(C,,)
Bxp
17 73 18 11
16q
18 11
9bz 15a,
18 79
1s: 7) 19 7
18 80
19 7
11
14q
19 60
10
8bz 13a1
20 96
20 1 22 0
12
9 8
7b2 12q
7
2106 24 83 24 86
6
lla,
5 4
lOal
28 57 38 77
3 2 1
6b2
38 90
9a1 562
39 46
801
39 78
22 0 25 0 25 0
39 21
*Adiabatic mmsatlon energlee bRef 73, He(I) ‘?hls work, He(I) (IE, = 13 82 eV, ref 73) dBand-maxlma at 15 8,16 2,16 5,17 6, and 18 3 eV eRef 29 Further references He(I), ref 55, lonemlsslon, refs 1, 2, laser-mduced fluorescence, ref 12, photon--photomn comcldence, refs 32,35, resonance electron capture, ref 36
1,2,3,4-Tetrafluorobenzene
C,jH2 F4 (C,,) HAM/3
1
3
27
2 402
26 25
2 4bl FCC) g 3bl WCC)
10 39 12 22
24 23 22 21
i? 16a, b 14b2 i% 15a* 13b2
13 13 14 15 15 15 15
W-’ WX)
10 10
Bxp 98
(9 6O)“.b
20 19 18
202 (nF)
17 16 15
2bl (‘IIF)
12b2 14al la2
13al
@F)
43 64 44 25 57 85 89
15 94 16 53 16 87
98 5 42)%’ 7 7 6 4d
12 (12 13 13 14 (15
1; 5)
e
311 1,2,3,4-Tetrafluorobenzene J
+
14 13
12 11 10 9 8 7 6 5 4 3 2 1
C&F4
(cp)-’
HAM/3
lb1 tnF) llbz 1201 lltll
17 36
(C,,)
1783 1832 1853 1904 2060 2063 2442 2442 2816 3859 3879 3913 3951
10bz
9bz lOa1 941
862 8a1 762 701 6bz 6~1
(contmued)
EXP 180 18 0 190 190 19 7 215 215 246 24 6
aAdlabatlc lonlsatlon enernes bRef 73, He(I) cRef 1, He(I)/lon-emuxnon dBandmaxuna at 15 5,16 1, and 17 2 eV =Ref 29 Further references He(I), ref 55, He(II), ref 59, lonemmuon, ref 2, pboton-photoion comcldence, ref 32,lasermduced fluorescence, ref 12 I, 2,3,5-Tetrafluoro J
*
benzene C!bHz F4 ( Czv )
(CPS’
HAM/3
EXP
27
2
26 25
2 2a2 okc) 2 461 @cc)
10
24 23 22 21 20 19 18 17 16 15 14 13 12 11
t? 12b2 fi 11b2 I 184~
13 37
13 6
1376 1445 1524 1557 1560 1617 1627 1630 1722 1737 1743 1811 1837
136 145 (155d
5bl (ncc)
lob2
9bz 3bl (KF) 1701 la2
@F)
2h
(ffF)
lb1
(TF)
1% ab2
7bz 15q
1007 44 1209
e 100 125 (1242)w
1' 0) 189 189
312 1,2,3,5-Tetrafluorobenzene I
C6H2F4 (C,,)
(conhued) Exp
HAM/3
Gzf w-’
10
14q
19 23
19 7
9
13al
20 59
211
8
6b2
20 63
216
7
5bz
24 41
24 7
6 5
12aI llal
24 42 28 13
24 7
4 3
lOa 9al
38 61 38 90
2
4bz
38 99
1
8al
39 41
aAdlabatlc lomsatlon ener@es bRef 73, He(I) CRef 1, He(I)/lon-emwslon dBandmaxnna at 15 5,16 0.16 5,17 3, and 17 7 eV eRef 29 Further references He(I), ref 55, He( II), ref 59,1on-emwlon, ref 2, photon-photoIon comcldence, ref 32, laser-induced fluorescence, ref 12 1,2,4,5-Tetrafluorobenzene 1
5
w-’
27
X 2blg (rcc)
C6H2F4 HAM/3 9 92
(D2h) Exp 95
(9 36)4b 10 2
26
A 2b3,(nx)
10 69
25
13 2b2, (ncc)
12 07
24 23
C 7&u
13 48 13 61
13 7 13 7 14 6 (15 4d
7hu
14 63 15 27 15 67 1588 16 02
8%
1611
22 21 20 19 18 17 16 15 14 13 12 11 10 9 8
5
9a,
E 6&g 8h.t %I lhg
tTF) (KF)
(10 04)“;b
4bzr
16 16 17 17 18 18 19 20
6%
20 60
14,
cTF)
W, lbzu 6h 5b3, 7% 6hu
(BF)
66 66 08 71 11 41 12 51
12 5 (12 35)“C
17 3) 17 9 17 9 18 9 18 9 19 5 210 216
e
313 1,2,4,5-Tetrafluorobenzene J
* 7
Cd H2 F4 (D2h) (contznued)
w’
HAM/3
4b3,
24 37
6
5bi,
24 43
5
5=g
28 11
4
3bzg
38 64
3
4bl,
38 69
2
3b3u
39 18
1
4%
39 26
Exp 24 8 24 a
aAdlabatlc lonlsatlon energies bRef 73, He(I) CRef 1, He(I)/lon-eml,won dBandmaxma at 15 5,15 7,16 1,16 4, and 17 0 eV eRef 29 Further references He(I), ref 55, He(U), ref 59, lon-emlsslon, ref 2, laser-Induced fluorescence, ref 12, photon-photolon comcldence, ref 32, resonance electron capture, ref 36 1,2,3-Trlftuorobenzene
(C,,)
HAM/3
J
$
24
z 4bl (WC)
23 22
C6H3F3
w-’
10 03
2
2a2 (~cc)
10 10
g
3h
12 20
(GX)
21
2
llb2
13 22
20
5 16~
19
i$ lob2
13 54 13 93
18
1521 1548
16
9bz 2bl (nF) 15al
15
14a1
16 01
17
14
la2
13
8b2
12 11
7b2
10 9 8
12al llal
7 6 5 4 3 2 1
lb1
(AF)
(nF)
13al
6b2 5b2 lOal gal 8=l 4b2 7=l
Exp
15 61 16 07 16 63 16 99 17 80
18 13 ia 41 20 20 20 20 24 01 24 04 27 38 38 39
17 2) 17 6
ia 4 ia 4 19 3 20 7 -20
7
24 24
76 46 80 23
Note added In proof aLaser-mduced fluorescence, V E Bondybey, J H Enghsh, T A Miller and R H Shlley, J Mol Spectrosc , 84 (1980) 124
314
1,2,4-Trzfluorobenzene C6H3 F3 (C,) w’
HAM/3
1
9
24
i 6a"(7rcc)
978
23 22
ii 5a"(Qc) ii 4a"(?lCc)
10 34
21 20 19 18 17 16 16 14 13 12 11 10 9 8 7 6 5 4 3 2 1
i? 27a' fi 26a’
1310 1340 1432 1531 1555 1560 1568 1609 1673 1691 1731 1806 1868 2015 2020 2400 2405 2772 3850 3869 3905
EXP 95
(9 3o)"'b 101 125 (12 3l)"'b 131 137 145 (154c
1206
E 25a’ 24a’ 23a’ 3a” (7t~) 22a’ 2a” (@) la” (?$)
21a' 20a' 19a’ 18a’
17a' 16a' 15a' 14a' 13a' 12a' lla' 100'
16 7) (17017 5) (179d18 6) 191 207 213 244 244
aAdlabatzc zonzsatlon energies bRef 1 cBand-maxmwm 18 1eV eRef 29 Further references
1,3,5-Trzfluorobenaene
lon-emlsslon, ref 2, photon-photolon
C&i3F3
--e (SCF)a
23,24 X 2e"(ncc)
1008
1114
22
1198
1511
1335 1373 1525
1601 1584 1817
5
w-’
at 16 0 eV dBand-maxlmum comcldence, refs 32, 35
(D3h) HAM/3
I
EXP 98 (9 64)b*c
ii 2aY (7rcc)
21 2 2ai 19,20 E 9e' 17,18 5 8e'
e
125 (1235)b" 13 6 136 154
e
at
316 1,3,5-TrQ7uorobenzene
C6H3 F3 (D3h) (contmued) HAM/3
--E (SCF)’
Exp
E le” (Q)
16 03
19 11
15 8
F la;’ (AF)
16 49
19 71
16 5
13
ii 7q E 7e’
19 79 19 45
17 0
11,12
16 82 17 10
10
7
1LT;
17 30
9
?
6a;
2150 2133
18 3 19 4
24 42
20 7d 21 3d 24 2
J
G w-’
15,16 14
7,8
6e’
18 88 20 16
5,6
5e’
24 00
29 28
4
5a;
27 68
33 33
4e’ 40;
38 73 38 81
2,3 1
17 3
aRef 58, mmunal-baslsset “ab mltlo” calculation bAdlabatlc lonlsatlon eneaes CRef 39, He(I) dBand-maxuna of Jahn-Teller durtorted 2E state (9) =Ref 29 Further references He(l), refs 33, 55, He(II), refs 59, 61, ion-em-on, refs 1, 2, laser-induced fluorescence, refs 12, 14, 15, 53 (also m sohd matnx, ref 15), resonance electron capture, ref 36, photon-photolon couwdence, ref 32 l,Z-Dzfluorobenzene
HAM/3
*
(P)‘-’
2
3h (ncc)
2
2a2
g
1341
13 77
16 28
(‘ITF)
15 21 15 35 15 50
(VF)
15 75 16 55
17 17 18 18 19 20 19
10bz
lllll
8bz 9al 8~1 7b,2 741 6bz
10 12 12 13
16 65 1762 17 19 19 23 23
90 67 79 63 68
Exp
10 52 10 86 14 58 14 97
9bz
lb1 lOa
9 74
--E (SCF)a
11 81 14 40
@cc)
E 2bl WCC) 5 11b2 I 12a1
la2
C6H4 F2 (C,,)
15 30
65 76 29 36 33 18 52
20 77 24 20 23 46
16 3) (16 ge li 18 20 20 23 23
9) 6 2 2 7 7
316 1,2-Lhfluorobenzene
C6 HqF2
(C,,)
HAM/3
@ w’
(contmued) --E (SCF)a
Exp
27 35
6~1
33 38
5bz 5a1
38 92
aRef 58, mmlmal-basis-set “ab mltio” calculation bAdlabatlc lomsatlon energies CRef 73 dBand maxma at 15 2,15 6, and 15 9 eV eBand maxuna at 17 1 and 17 6 eV Further references He(I), ref 55 1,3-Lhfiuorobenzene *
(cp)-’
2
202
(ncc)
x 3bl @cc) fi
2bl @cc)
E 14a1 5 lob2 ii? 9bz 13al 12Ul 142
(EF)
lb1
(TF)
8b2
lla1 lOi lOal gal 6bz
C6H4FZ (C,,) HAM/3 9 76 10 08 12 04
10 54
Exp 95
10 88
(9 32)b” 10 0
14 91
(9 68)’ 12 4
1295 13 35 13 68
14 73 15 33 16 48
1503 1544
(12 -12 13 -13
22)b.d 9 6 6
53 94 65 07 71 24
(14 8f I
16 31 16 54
17 17 18 19 18 19
16 92
20 33
17 7)
18 18 19 67 19 75
20 80
18 6 20 2
15 87 16 18
801
23 61 23 68
7a1 4bz 6al
27 31 38 59 38 63
5b2
--e (SCF)a
485e
1290e 970e
20 2 23 7 23 7
aRef 58, mmlmal-basis-set “ab mltlo” calculation bAdlabatlc lomsatlon energies ‘Ref 73, He(I) dRef 2, He(I)/lon-emlsslon e This work, high-resolution He(I) spectrum fBand-maxlma at 15 0,15 6,16 4,17 0, and 17 4 eV Further references He(I), ref 55, photon-photolon comcldence, ref 32
317
1,4-Dzfluorobenzene CgH4Fz (D2h) HAM/3
@ w-’
X %g @cc) A lh,
Okc)
B 4bzg
E 2bu
(ncc)
D 5b3,
E
8ag
%u 7blu 3bzg lb, (RF) lbu (nF)
Gp
--E(SCF)~
EXP 420f (9 14)e*f 1355f 101 (1003yvf 1450f 12 5 (1209)e*f 125 13 7 14 3 (14gg
9 50
937
10 39
1027
1002
1106
1249
1277
1433
1193 13 20 14 34 1507 1566 1500 1576 1595
12 61b" 1412 1438 1539 1581 1596 1681 17 87b" 1974 2020 1796
1645 1808 1730 19 59 19 58 2349
2b3,
2370
5%
2728
4blu
3797
4%
3798
1820 1873 2126b 2148 2213b 2258 2527b 2655 2683 2670b 2699 2711 2935b 3043 3055 3081 4131 427zb 4273 4287 4237b 4262 4271 4284
(0 76)
1488 1590 1642 1747 1791 1781 1864
(0 77) (0 070,o093) (0 064,O067) 2035
(0 24) (0 53) (0 54) (0 11) (0 15) (0 39) (0 18) (0 26) (0 17) (0 25) (0 05) (0 42) (0 11) (0 05) (0 95) (0 58) (0 19) (0 074)
1966 2075 2328
94
16 5) 805f 169 (1676)e*f 805f 172 (1713)"f 18 0 180 202
2431
-209
2854
239
2902
23 9
(005) (0 057) (047) (0 20) (contrnued
overleaf)
318 aBasls set (9s5p/4s), compare also ref 56 bTamm-Dancoff Green’s function results, relatwe intensities pven m parentheses ‘?I’he Green’s function IS non-diagonal in the lblu (q?) and 2bz,, (ffcc) orbltals This non-diagonal character fmds its major expresslon m the mtentnty-borrowmg mechsnlsm for the two satelhte hnes of largest relative mtensltles The two relative mtensltles which are given refer to the sunple hole-states 1 bzu and 2bzu In such a case, a statement about the mtensltles of a band can only be made d the dipole matrix elements are calculated This has not been done dRef 58, mmunal-baslsset “ab m&lo” calculation eAdlabatlc lomsatlon energies f This work, high-resolution He(I) spectrum sBand-maxlma at 15 16 and 15 5 eV Further references He(I), refs 33,55, 74, He(H), ref 59, resonance electron capture, ref 36 Fiuorobenzene
CgHsF HAM/3
+
w-’
2
3bl 6x)
2
la2
5
8bz
9 62
(C,,) --e (SCF)a 10 15
10 03 12 49
10 5
z 2bl @cc) 5 13Ul B 7bz
12 08 13 14 13 62
14 75 14 75 16 06
F 6b2 G 12q
14 91 16 26
17 08
ii 6bz
15 81 15 86 16 38
7
lb1 llal 1oq
(ncc)
(KF)
14 06
17 36 19 08 18 37 18 56
Exp 94 (9 22)b” 98 12 3 (11 79)b*d 12 3 13 13 (13 14 15 16
0 9 89)b*d 6 2 4
16 16 17 (17
4 4 7 67)b*d
17 37
20 30 23 65
%
19 20 19 24
8~1
23 2’7
22 85 28 14
23 3
3b2
23 43
28 50
23 3
27 04 37 97
32 22
4bz
7al 6~1
1370d 490d
19 7 19 7
aRef 58, mmlmal-bass-set “ab mltlo” calculation bAdiabatlc lomsatlon enewes CRef 69, He(I) angular dlstrlbutlon (ref 73, 9 19 eV) dThls work, high-resolution He(I) spectrum He(I), refs 31, 33, 55, 74, He(I) angular dlstrlbutlon, ref 67, Further references resonance electron capture, ref 36, ion photodlssoclatlon, ref 34
319 Hydrogen
fluorzde
HF (CL,)
6
w-’
HAM/3
lWPTa
GFb
z
In
16 81
16 16
1626
(0 94)
ii 30
19 80
19 73
72 29’ 20 Ogc
(0 038) (0 95)
(16 039)d*e 19 9
73 37
(0 030)
(19 118+”
ii 20
39 65
37 99’ 4097 43 00 10134
EXP
(0 (0 (0 (0
52) 35) 052) 031)
16 19
g h
39 6f
aRef 26 bBasls set [lls7pld/6slp] + (5s4pld/3slp) cTamm-Dancoff Green’s functlon results, basis set [9s5p/4s] + (4s2p/2s), relative mtensltxes gwen m parentheses dAdlabatlc lomsatlon energies eRef 40 threshold photoelectron spectrum ‘Ref 5, Mg KLY, Y Mt radlatlon %, = 3090 5 cm 4 , w&. = 89 cm-‘, ref 38 h~, = 1496 1 cm-‘, ueXe = 88 4 cm-‘, ref 38 Further references He(I), refs 8, 18, 50, 75, He(II), ref 18, 1on-emwslon, ref 38, (e,2e) ref 17, electron energy-loss spectroscopy, ref 65 Fluorme
Fz (D-h) HAM/3
RSPT’
GFb
EXP
i? 1 ng (TF-)
16 36
15 66
15 86
1587 (15 7O)d’”
i
19 40
18 69
18 99
20 40
20 80
2103
9
z
w-l
1% (w+) 3us
2; 20, i? 20,
36 36 42 43
1050e
18 8 21 If
28 87’
(0 11)
3617
(0 71)
40 53’ 4130
(0 56) (0 13)
56 19
(0 13)
aRef 25 bRef 57, basis set (lls7p2d) CTamm-Dancoff Green’s function results, relatwe mtenslttes given m parentheses dAdlabatlc lomsatlon energies =Ref 27 f Ref 11
Supplementary
References
1 M Allan and J P Maler, Chem Phys Lett ,34 (1975) 442 2 M Allan, J P Maler and 0 Martbaler, Chem Phys ,26 (1977) 131 3 M Allan, J P Maler, 0 Martbaler and J P Stadelmann, J Chem Phys ,70 (1979) 5271 4 G de Alto, P Decleva and A Sgamelottl, J Electron Spectrosc Relat Phenom ,12 (1977) 249 5 M S Banna and D A Shirley, Chem Phys Lett ,33 (1975) 441 6 M Barber. J D Clark, A Hrnchhffe and S Mann, Chem Phys L&t, 44 (1976) 526
7
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43
J Bastlde, D Hall, E Hedbronner, J P Maler and R G Plevey, J Electron Spectrosc Relat Phenom , 16 (1979) 205 J BerkoHntz, Chem Phys Lett , ll(l971) 21 G BIerI, E Hetibronner, V Hornung, E KlosterJensen, J P Maler, F Thommen and W von Nlessen, Chem Phys , 36 (1979) 1 G BIeri, E Hellbronner, J P Stadelmann, J Vogt and W von Nlessen, J Am Chem Sot, 99 (1977) 6832 G BIerI, A Schmelzer, L &brmk and M Jonsson, Chem Phys ,49 (1980) 213 V E Bondybey and T A Miller, J Chem Phys ,70 (1979) 138 V E Bondybey and T A Miller, J Chem Phys ,73 (1980) 3053 V E Bondybey, T A Miller and J H English, J Chem Phys ,71(1979)1088 V E Bondybey, T J Sears, J H Enghsh and T A Miller, J Chem Phys ,73 (1980) 2063 B Brehm, R Frey, A Kustler and J H D Eland, Int J Mass Spectrom Ion Phys , 13 (1974) 251 C E Brlon, S T Hood, I H Suzuki, E Welgold and G R J Williams, J Electron Spectrosc Relat Phenom , 21 (1980) 71 C R Brundle, Chem Phys Lett , 7 (1970) 317 C R Brundle, M B Robm and H Basch, J Chem Phys, 53 (1970) 2196 C R Brundle, M B Robm, N A Kuebler and H Basch, J Am Chem Sot ( 94 (1972) 1451 C R Brundle, M B Robm and N A Kuebler, J Am Chem Sot ,94 (1972) 1466 W E Bull, B P Pullen, F A Grimm, W E Moddeman, G K Schweitzer and T A Carlson, Inorg Chem ,9 (1970) 2474 T A Carlson and R M White, J Chem Sot , Faraday Discuss , 54 (1972) 285 N S Chm, P D Burrow and K D Jordan, Chem Phys Lett ,68 (1979) 121 D P Chong, F G Herrmg and D McWlllrams, J Chem Phys ,61(1974) 3567 D P Chong, F G Herrmg and D McWllhams, J Electron Spectrosc Relat Phenom , 7 (1975) 429 A B Cornford, D C Frost, C A McDowell, J L Ragle and I A Stenhouse, J Chem Phys , 54 (1971) 2651 C Cossart-Magos, D Cossart and S Leach, J Chem Phys ,69 (1978) 4313 C Cossart-Magos, D Cossart and S Leach, Mol Phys ,37 (1979) 793 J Dannacher, A Schmelzer, J P Stadelmann and J Vogt, Int J Mass Spectrom Ion Phys, 31(1979) 175 T P Debles and J W Rabalals, J Electron Spectrosc Relat Phenom , 1 (1972/73) 355 G DuJardm, S Leach and G Taleb, Chem Phys , 46 (1980) 407 C B Duke, K L Yip, G P Ceasar, A W Potts and D G Streets, J Chem Phys (66 (1977) 256 R C Dunbar, H Ho, I Teng and E W Fu, J Am Chem Sot ,101(1979)6506 J H D Eland, M Devoret and S Leach, Chem Phys Lett ,43 (1976) 97 J R Frazier, L G Chnstophorou, J G Carter and H C Schwemler, J Chem Phys , 69 (1978) 3807 U Gehus, J Electron Spectrosc Relat Phenom , 5 (1974) 985 S Gewurtz, H Lew and P Flanek, Can J Phys ,53 (1975) 1097 R GIlbert, P Sauvageau and C Sandorfy, Chem Phys Lett , 17 (1972) 465 P Guyon, R Spohr, W A Chupka and J Berkowitz, J Chem Phys , 65 (1976) 1650 H J Hamk, E Hellbronner, V Hornung and E KlosterJensen, Helv Chum Acta, 53 (1970) 1073 W R Harshbarger, M B Robin and E N Lassettre, J Electron Spectrosc Relat Phenom , 1 (1972/73) 319 E Hellbronner, K A Muszkat and J Schaeublm, Helv Chum Acta, 54 (1971) 58
321 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 6.5 66 67 68 69 70
71 72 73 74 75 76
H W JochlRls, W Lohr and H Baumgartel, Nouv J Chum ,3 (1979) 169 A E Jonas, G K Schweitzer, F A Grimm and T A Carlson, J Electron SPeCtrosc Relat Phenom , 1 (1972/73) 29 L Karlsson, R Jadrny, L Mat&on, F T Chau and K Slegbahn, Pbys Scr , 16 (1977) 225 T Kobayashl and S Nagakura, J Electron Spectrosc Relat Phenom ,7 (1975) 187 R F Lake and H Thompson, Proc R Sot London, Ser A, 315 (1970) 323 S R Langhoff and D P Chong, Chem Phys, 55 (1981) 355 I-I J Lempka, T R Passmore and W C Price, Proc R Sot London, Ser A, 304 (1968) 53 D R Lloyd and P J Roberts, J Electron Spectrosc Relat Phenom , 7 (1975) 325 J P Maler, 0 Marthaler and G Blen, Chem Phys ,44 (1979) 131 T A Mdler and V E Bondybey, Chem Phys Lett ,58 (1978) 454 J Mueller, E Poulam, 0 Goscmskl and L Karlsson, J Chem Phys , 72 (1980) 2687 B Narayan and J N Murrell, Mol Phys , 19 (1970) 169 W von Nlessen, G H F Dlercksen and L S Cederbaum, Chem Phys Lett , 45 (1977) 295 W von Nlessen, G H F Dlercksen and L S Cederbaum, J Chem Phys ,67 (1977) 4124 M H Palmer, W Moyes, M Splers and J N A Rldyard, J Mol Struct ,49 (1978) 105 A W Potts, W C Price, D G Streets and T A Wimms, J Chem Sot , Faraday DlSCUss,54 (1972) 168 I POWIS, Mol Phys ,39 (1980) 311 W C Price, A W Potts and T A Wllhams, Chem Phys Lett , 37 (1976) 17 B P Pullen, T A Carlson, W E Moddeman, G K Schweitzer, W E Bull and F A Grimm, J Chem Phys ,53 (1970) 768 V D Remke, H Baumgartel, T Cvlti, L Klasmc and M Gusten, Ber Bunsenges Phys Chem ,78 (1974) 1145 D Remke, R Kraesslg and H Baumgartel, Z Naturforsch , 28a (1973) 1021 A Salama and J B Hasted, J Phys B, 9 (1976) L333 (see C E Brlon and A P Hltchcock, rbld , 13 (1980) L677 for dlscusslon) P Sauvageau, J Doucet, R Gilbert and C Sandorfy, J Chem Phys ,61(1974) 391 J A Sell and A Kuppermann, Chem Phys ,33 (1978) 367 J A Sell and A Kuppermann, J Chem Phys ,71(1979)4703 J A Sell, D M Mmtz and A Kuppermann, Chem Phys Lett ,58 (1978) 601 K Slegbahn, C Nordhng, G Johansson, J Hedman, F P Heden, K Hamrm, U Gehus, T Bergmark, L 0 Werme, R Manne and Y Baer, ESCA Applied to Free Molecules, North-Holland, Amsterdam, 1969 I G Slmm, C J Danby, J H D Eland and P I Mansell, J Chem Sot , Faraday Trans 2,72 (1972) 423 J P Stadelmann and J Vogt, Int J Mass Spectrom Ion Phys ,35 (1980) 83 D G Streets and G P Ceasar, Mol Phys ,26 (1973) 1037 D W Turner, C Baker, A D Baker and C R Brundle, Molecular Photoelectron Spectroscopy, Wiley-Intersclence, London, 1970 T E H Walker, P M Dehmer and J Berkowtz, J Chem Phys ,59 (1973) 4292 T Yamazakl, S Katsumata and K Klmura, J Electron Spectrosc Relat Phenom ,2 (1973) 335
ACKNOWLEDGEMENTS
This work has been supported by the SWISSNational Science Foundation (Part 135 of ProJect No 2 012-079, for Part 134, see ref 1) and by the
Swedish Natural Science Research Council One of us (G B ) would like to express his gratitude to the Swiss National Science Foundation for the grant of a fellowship. Financial support by Clba-Gelgy SA, F Hoffman-La Roche & Cle, Sandoz SA, and the Fonds der Deutschen Chemlschen Industne 1s gratefully acknowledged Finally we would like to thank Dr J P Maler and Mr P For&r (Umverslty of Basel) for the gft of some samples of fluoro-substrtuted benzenes, and Prof K. Slegbahn and Dr L Karlsson (Umverslty of Uppsala) for the probes of methyl fluonde and fluoroform. Last but not least we are obhged to Prof E Lmdholm (Stockholm) for thorough mspectlon of the manuscnpt
REFERENCES 1
2
3 4
5
6 7 8
W von Nlessen, G Btert and L kbrtnk, J Electron Spectrosc Relat Phenom , 21 (1980) 176 L &bnnk, C Fndh and E Ltndholm, Chem Phys Lett , 52 (1977) 63, 69, L Lbrmk, C Fndh, E Lmdholm, S de BrlliJn and D P Chong, Phys Scr , 22 (1980) 475 L S Cederbaum,Theor Chun Acta, 31(1973) 239, J Phys B, 8 (1975) 290 L S Cederbaum and W Domcke, Adv Chem Phys, 36 (1977) 205, J Schlrmer, Thesis, Techntcal Umverslty, Munich, 1977, J Schumer and L S Cederbaum, J Phys B, ll(l978) 1889 G BIerI, J P Stadehnann, F Thommen and J Vogt, Helv Chum Acta, 61 (1978) 367, G Bieri, Conf Proc , 4th Int Symp on Plasma Chemistry, 1979, Vol 2 (S Vepgek and J Hertz, Eds ), p 467 (Chem Abstr ,92 57952r) Houben-Weyl, Methoden der Organlschen Chemte (Halogensverbtndungen), Band V/3 (E Muller, Ed ), G Thteme Verlag, Stuttgart, 1962, pp 166,206 L M Denms, J M Veeder and E G Rochow, J Am Chem Sot ,53 (1931) 3263 C Cossart-Magos, D Cossart and S Leach, Mol Phys ,37 (1979) 793
Data bank
30.4-1~1 He(II) PHOTOELECTRON MOLECULES Part IV. Fluoro-compounds
SPECTRA OF ORGANIC
(C, H, F)*
GERHARD BIERI? Physrkahsch-Chemrsches Instztut der Unwersrtat Base& Klmgelbergstrasse 80, CH-4056 Base1 (Swrtzerland} LEIF ASBRINK The Royal Institute of Technology, Physrcs Department, S-100 44 Stockholm (Sweden)
70
WOLFGANG VON NIESSEN Instltut fur Phyakahsche Chemle, Technrsche Universltat Braunschwerg, Hans-SommerStrasse 10, D-3300 Braunschwelg (W Germany) (Received
5 January 1981)
REMARKS
Part IV of this Data bank IS concerned ~th the He(I1) photoelectron spectra of 30 fluoro-compounds, mcludmg all fluoro-denvatlves of methane, acetylene, ethylene and benzene, The assignment of the observed bands 1s obtamed from semlemplrlcal HAM/3 calculations [2 1, from many-body Green’s function calculations [3] combmed urlth Tamm-Dancoff Green’s functron calculations [4] for the mner valence regon, and/or from other types of calculations published previously The calculations are complied m the Tables together ~th the expenmental lomsatlon energes The 30 4-nm He(H) photoelectron spectra axe shown m the followmg Figures (abscissa scale m eV, ordmate gwes count-rate m arbitrary units For other delis, see Part I**) The spectra of closely related molecules are presented together on one page The ordermg according the sum formula has therefore not stnctly been followed * For Part III, see ref 1 *i Present address The Royal Institute of Technology, Stockholm, d Electron Spectrosc Relat Phenom , 20 (1980) 149 0368.2048/81/0000-0000/$02
50 o 1981
Ekevler Sclentlflc
Sweden
Pubhshmg Company
282
He
CF 4
CHF,
283
r,
I,
I
25
I
I
I,
20
15
10
F-C’=C-F
25
20
15
10
H-CC-F
+++,
25
20
15
10
285
F
F
I
(filtered spect rum) b
20
25
30
F
10
15
F \ F
11
11
25
‘1
’
1
20
”
‘1
I
15
’
“‘I”
10
286
F
F
-I /-
15
10
15
10
F
F
25
20
287
25
F /
288
,
I
I,,
25
I,
1
I,
20
CF,-CEC-H
I,,
,
15
,
,
,
1
,
10
289
F-CzC-CsC-F
CF3-CX-CX-F
I
25
290
F
F F
0
F
0
25
F
20
15
10
F F F ti
I
11
III
25
F 0
F
1,
I1
20
I1
11
15
1
f
II
I
10
I
291
25 F
0 0
F
F
F
:I
292
F F
1,
I
25
I
Ex F
F
I
I
(
20
11
1
’
(
15
I”’
1’1
10
7
293
25
15
20 F
v 0
F
F
i
I
d
4
v
:
294
F
25
II
(
25
15
20
I
I
I7
11
20
1
11
11
15
10
1
c
“I’
10
295
F
0 0
F
F
0 0
HF
25
I
I
I
,
25
20
I,
,
I,
15
1
20
,
(
,
15
10
297
EXPERIMENTAL
Samples CF,, C2 F, , C2 F4, CZ HF, C4 F, and C5 F, were obtamed from electrical discharges m vapours of a smtable substrate, as outlined m ref 5. The samples were purified by bulb-to-bulb &stfilatlon, momtored by He(I) spectroscopy. CH2 Fz and CZH5 F were syntheslsed accordmg to the method outlmed m ref 6 HF was obtamed from heated KHF, salt and F, was prepared from electrolysis of molten KHF, [ 71 1,2,3-Trlfluorobenzene was kmdly supplied by Dr J P Maler and Mr P Forster (University of Basel) All other samples were of commercial origm Spectra The spectrum of tetrafluoroethylene was obtamed by usmg filtered He(I1) radiation A thm polystyrene film was placed between the light source and the lomsation chamber. The 58.4-nm hne of the He(I) rachatlon was reduced by a factor of 104, whereas for He(I1) ra&atlon a transmlsslon of -10% was obtamed
TABLES
Stu te speczfzca tzon, orbs tul no ta tzon r-type charactensed by =cc TF
orbltals are supplementarily
acetylemc, ethylemc or benzemc r-orbital out-of-plane fluorme lone-pm orbital
+ or - speclfles the sign of the correspondmg hnear combmatlon for molecules with Dmh , CZh or CZV symmetry (except fluorobenzenes) An additional guide for the speclflcatlon of the electronic states 1s gwen by the valence orbital number J, which 1s mtroduced for large molecules (C, Fq, C6 Fe, Cd%, GA F4 and G Hs F3 ) Ionzsatzon energzes and uzbratzonal frequenczes For overlappmg bandsystems which cannot unambiguously be assigned, the band area 1s Dven This 1s mdlcated by open parentheses The observed vibrational progressions m the photoelectron spectra of the fluorobenzenes are not included m the Table A vlbromc analysis IS more accurately obtamed from ion-emlsslon spectra For a summary, see ref 8 References The references m the footnotes below each section of the Table are complied m the Supplementary References (alphabetical by author), pp 319-321
298
VALENCE IONISATION ENERGIES (eV) AND OBSERVED VIBRATIONAL GRESSIONS (cm-’ )
Carbon tetrufluorde + W-l
2
PRO-
CF4 (Td ) HAM/3
U(SCF)’
Exp
It1
16 46
16 50
16 2
ii 4t2 ii le
17 26 18 16
(17 51)b 20 60
17 4 18 5
2; 3t2
2166
24 00
fi 4a1
24 71
27 26
2t2
4100
301
44 54
810e
(18 30)ae
400 645e
43 87c
22 1 (217O)k” 25 1 (25 12)d 40 3f
49 50
43 Bf
730=
*Ref 54, symmetry-unrestricted (C,) ab mltlo Hartree-Fock calculation bNot converged c a’ symmetry, a” at 44 87 eV dAdlabatlc lomsatron energies eRef 19, He(I)/He (II) fRef 5, MgK(Y,YM{ radlatlon Further references He(I), refs 22, 45, 62, 74, He(I) angular dlstnbutlon, ref 23, He (I)/He(II), ref 51, photoelectron-photolon comcldence, refs 16, 60, 71, Mg Kcwradlat&on,ref 70, Al Karradlatlon, ref 37, electron energy-loss spectroscopy, ref 42 Fluoroforrn
CHFJ (C,,)
G w’
HAM/3
MS-X(&*
g 6a1 ii la2 ii 5e
14 94 15 71 16 16
15 56 17 41
2; 4e
17 00
17 10 18 68
G 3e
20 47
2141
i!Z Sal F” 441
20 81 24 70
20 08 23 93
2e 3ul
39 78 42 22
36 56 38 80
Exp 14 8 15 5 16 2 17 2 (17 o@c 20 7
1030c 570 480
(20 oo)b*c 20 7 4e 42)bC 15f 0’
24 (24 39 42
2660d 1050
aRef 4 bAdlabatlc lomsatlon energies =Ref 74 dThls work =Due to mcreased pressure, no He peak at 24 6 eV was found m this experrment ‘Ref 5, Mg Ka, Y MS radlatlon Further references He(I), ref 62, He(I) angular dlstnbutton, ref 23, He(I)/He(II), ref 19, electron energy-loss spectroscopy, ref 42
299 MethyZene fluonde
CH2 F2 (C,,)
5
HAM/3
MS-Xc?
FOCI + Qb
13 06
14 18
13 31
(VP
a% 2b,
EXP 13 3
1120d
(12 74)c’d ii
15 05
154
15 67
1697 16 11
15 38
154
1576
1763
15 83
4b2
15 46
B 6a, E la2
15 8 (15 58)c*d 19 1
19 22
18 72
18 05
i% 3b2 F 5aJ
19 17 19 33
19 69 18 77
18 90 18 79
G 4q
24 05
22 89
24 0
38 45 39 95
36 33 37 28
38 2’ 40 If
980d 480 680d
(18 31)=
2b2 3a1
19 1 19 1
aRef 4, compare aiso ref 6 bRef 49, frozen-orbhal CI + quadruples corrections CAdlabatlc lomsatlon energies dRef 74, He(I) eRef 62, IE, = 18 17 eV f Ref 5, Mg KCU, Y k?{ radiation Further references He(I)/He(II), ref 19, He(I) angular dwtnbutlon, ref 23, electron energy-loss spectroscopy, ref 42 Me thy2 fluonde
CH, F ( C!J”)
G OP-’
HAM/3
MS-Xcta
GFb
if
2e
13 16
13 96
13 39
(0 94)
z
5q
18 23
17 60
16 88
g lf?(aF) E 4a,
17 50 23 48
18 77 2186
17 19 23 82’ 28 65
(0 93) (0 92) (0 84)
301
38 26
37 70
EXP 13 1 (12 54)d’”
1290e 880 695
17 0 17 0 23 4
(0 021)
34 53
(0 030)
36 87’
(0 032)
37 80 37 81
(0 11) (0 046)
38 23 38 66 40 58
(0 16) (0 31) (0 03i)
42 38 42 75
(0 083) (0 035)
38 4’
aRef 4 bBasls set (9sSp/4s), relative mten&es qven m parentheses ’ 2ph-Tamm-Dancoff Green’s fun&on results, the (e)-’ states are calculated to be non-&agonal (2e)-’ = 13 00 eV (0 037,O 89), (Is)-’ = 17 10 eV (0 87, 0 042) dAdlabatlc Jon&&Jon energy eRef 46 fRef 5, Mg K&, Y MS radlatlon Further references He(I), ref 62, He(I)/He(II), ref 19, He(I) angular dlstnbutlon, ref 23, electron energy-loss spectroscopy, ref 42
300 Difluoroace ty lene C2 F2 ( Dmh)
* w
HAM/3
2
11 a2
2% (ncc)
STO-3G
GFa
8 49
1131
EXP 1160 (11 18)@
2420f 825
(11 49)e .i
lTr, (RF_)
B 1% E 50s 5
(nF+)
40,
B 40,
17 11
1598
18 14
17 7
17 74
1709
18 62
18 5
19 93
17 87
20 74
20 6
2199
19 33
20 57b
(0 55)
217
26 62
2120 25 05b
(0 33) (0 095)
25
26 13
3%
40 84
3%
4143
43 15
43 19
25 72
(0 44)
27 48
(0 23)
30 60
(0 11)
40 94b
(0 45)
42 17 42 47
(0 16) (0 062)
40 6gb
(0 20)
4185 43 37
(0 33) (0 083)
&Bas= set (9s5pld) bTamm-Dancoff Green’s function results, relative mtenshes given m parentheses CAdlabatlc lomsahon energy dRef 10, He(I) eMost mtense peak of VIbratlonal progresslon f Ref 11, He( II)
Tefrafluoroethylene
C2F4 (DZh)
G (FT’
HAM/3
STO-3G
GFa
x
10 71
7 50
1110
f&u (‘kc)
EXP 10 69 (10 14)c*d
1690f 740
(10 56)e
A 4b3,
16 06
13 65
16 62
159
6a, i? 4bzU
16 25
12 72
16 75
16 6
16 22
13 63
17 04
16 6
5
16 34
14 24
17 27
166
16 41
14 32
17 42
16 6
17 31
15 10
18 12
g
k(nF)
17 6
740f
(17 51)&d
G lbzg (nF) H 3b3,
17 68
16 25
18 87
19 71
16 31
19 74
18 2 19 4 (19 19)Sd
7
lb,
3bzU ii: 5ag
2
('llF)
19 36
18 26
20 14
194
20 25
18 56
2130
210
20 50
19 19
2184
210
660’
301 Tetrafluoroethylene
C2F4 (DZk)
(contrnued)
w-’
HAM/3
STO-3G
GFa
L 4blu
22 54
20 53
22 51b
(0 35)
22 74
(0 28)
23 40
(0 25)
27 94b
(0 53)
29 78 3157
(0 13) (0 084)
42 46b
(0 065)
42 68
(0 51)
43 59 42 70b
(0 05) (0 091)
43 11
(0 55)
43 49
(0 05) (0 083)
s
ii!? 40,
2hs
262,
3bl,
3nl?
27 35
26 63
4154
40 08
41 a4
39 99
43 22
40 96
42 10
43 70
44 24b
EXP
44 45
(0 13)
44 64
(0 13)
44 67
(0 08)
44 71
(0 062)
44 94
(0 07)
45 45 44 3gb
(0 05) (0 068)
44 71
(0 058)
44 78 44 91
(0 13) (0 063)
45 23
(0 14)
45 64
(0 097)
22 5
26 3
'Basis set
(9s5p) b Tamm-Dancoff Green’s function results, relative mtensltles pven m eMost intense peak of parentheses CAdlabatlc lomsatlon eneraes dRef 20, He(I)/He(II) vlbrahonal progresslon f Ref 48, He(I) Further references, He(I) angular dlstnbutlon, refs 68, 69, CNDO/SS, ref 33, resonance electron capture, ref 24
Fluoroacetylene
CzHF
(CL,)
+ w’
HAM/3
2 2n(7kc)
1168
STO-3G
GFa
9 00
1134
EXP 11 50 (11 26)c’d
ii
70
la 28
17 23
18 12
la 0
ii
Ia
17 56
16 68
18 31
18 0
?
60
21 23
19 33
2114
212
5
50
25 11
26 28
24 85b
(0 47)
26 52
(0 15)
29 67
(0 24)
24 3
21aod 1210
302 Fluoroacetylene
CzHF
@ (d-’ 4a
(G,)
(contmued)
HAM/3
STO-3G
GFa
4125
43 25
40 8gb
(0 17)
42 04
(0 28)
EXP
42 79
(0 12)
43 40
(0 11)
aBaw set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles gwen m parentheses CAdlabatlc lomsatlon energy dRefs 41,43, He(I) Trffluoroethylene
C2HF3 (C,)
+ (P)--’
HAM/3
2 40” @cc)
10 48
STO-3G 7 85
GFa
EXP 10 62
10 81
(10 14)c’d (10 54)e 14 86 15 62 16 01
12 24
16 58 16 57 18 26
14 01 14 81
E la” (77~) ii 12a’
18 52
7
2 16a’ Z 15a’ E 3a” (RF) ii 14a’ i% 2a” (71~) F 13a’
lla’
3 104’ i7 9a’ 8a’ 7a’ 60’
13 34 14 02
14 7 16 0
1502 16 42
-16
16 94
5
16 8 16 8
1534
17 08 17 36 18 26
1723
19 22
19 44
17 61
20 28
18 7 20 1
19 75
la 77
20 54
2193 25 95
20 57 27 13
23 06b 27 34b
(0 37) (0 09)
28 60
(0 46)
39 24
4126 4161 43 13
39 56 4121
18 0
20 1 219 25 8
aBasls set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensitles given m parentheses CAdlabatlc lonlsatlon energy dRefs 68, 69, He(I) angular dlstrlbutton eMost intense peak of vlbratlonal progression Further references resonance electron capture, ref 24 l,l-DQ’luoroethylene
CzHzF2
(C,,)
HAM/3
STO-3G
2 261 (mcc)
10 59
ii 5b2
14 83
+
w-’
GFa
EXP
8 25
10 77
13 25
15 33
10 (10 (10 14 (14
70 29)c’d 69)e 9 06)Cf
1600’ 720 1180’
303 1,l -D$luoroethybne
CzH2 F2 (C,,)
(continued)
+
w’
HAM/3
STO-3G
GFa
5
8U' 4bz
15 80
13 10
15 81
15 8
16 00
16 07 16 52 18 49
16 1 16 1 18 2 19 7
E
b 102 (BF-) Z 7al
16 03 18 25
14 31 13 90 17 47
F 161 (nF+) i? 3b2
18 20 19 60
16 96 17 83
18 71 19 89
fi 6al ‘i 5q
2153 25 41
20 41 27 07
21 83b 25 93b 27 29 29 86 30 80
262
39 37
4130
41 52b 4182 4187 4196 42 20 42 31 42 54
43 22
4al
43 67b 43 92 44 22 44 43 44 66
EXP
18 2
(0 37) (0 21) (0 45)
21 5 25 2
(0 05) (0 (0 (0 (0 (0 (0
06) 04) 20) 12) 077) 073)
(0 071) (0 11) (0 37) (0 085) (0 069) (0 096) (0 063)
abash set (9s5p/4s) bTamm-Dancoff Green’s function results, relatwe mtensltles given m parentheses CAdlabatlc lomsatlon energres dRefs 68, 69, He(I) angular dlstrlbutlon eMost intense peak of vIbrational progression ‘Ref 48, He(I) Further references He(I), ref 74, photolomsatlon, ref 64, resonance electron capture, ref 24 as-1,2-Dzfluoroethylene 3
(VP
2 2ht @cc)
C2H2 Fz (C,,)
HAM/3
STO-3G
10 25
7 81
GFa
EXP
10 54
10 62 (10 22)=-d
1600df 1330
(10 63)e
1030 250
AT 7aj
13 97
1171
14 30
ii 6b2
15 28
13 02
15 16
14 0 1430d (13 79)CA 1020 240 14 9 (14 89)Gd
304 cls-I,P-LWluoroethylene G w-l
C$N, Fz (C,,)
(contmued)
HAM/3
STO-3G
GFa
16 12
16 64
16 2
17 28
14 33 15 01
17 20
17 1
17 04
15 66
17 41
17 1
18 32 18 72
16 36 18 44
18 84 19 34
18 8 18 8
21 28
20 39
21 OBb 2140 26 06b
25 28
26 76
27 33 39 15
3bz
4131
30 06 41 03b 4115 4161 4163 42 03
39 55
34
4167
42 18 41 73b 42 03 42 15 42 37
EXP
(0 70)
20 9
(0 15) (0 37)
25 2
(0 (0 (0 (0
31) 054) 075) 052)
(0 063) (0 17) (0 18) (0 083) (9 16) (0 057) (0 15) (0 24)
aBas~ set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles given m parentheses ‘Adlabatlc lonwatlon energies dRef 52, Ne(I)/lon-emwon eMost intense peak of vlbratlonal progression f f 10 cm-’ Further references He(I) angular dlstrrbutlon, refs 68, 69, synchrotron radiation, ref 44, photoelectron-photoloon comcldence, ref 72, resonance electron capture, ref 24 trans-1, P-Dzfluoroe thylene CZHz F2 (C&h) 5
w-’
HAM/3
2
2% @cc)
10 11
STO-3G 7 82
GFa 10 57
EXP 10 63
1650d
(10 21)C*d 1280 ii 7a,
13 79
1182
14 28
ii 6b,
15 11
13 03
15 39
16 17 17 18 18
14 14 15 17 17
1668 1703 17 37 19 00 19 10
e 5 2 Z G
lb, (RF-) 6a, 1% 5ag 5b,
(nF+)
14 41 09 41 63
19 30 50 64 07
(10 14 (13 15 (15 16 17 17 18 18
61)e 0 51)C.d 1 09)C’d 3 0 0 8 8
530 530d
305 trans-l,Z-Dlfluoroethylene
CZHz F,
(C,,)
(contrnued)
G w
HAM/3
STO-3G
GFa
i7
2137
20 89
20 81b
(0 12)
2109
(0 17)
2148
(0 54) (0 088)
48,
‘i: 4as
3bu
25 06
38 68
26 59
4123
25 3gb 25 83
(0 078)
26 00 26 37
(0 11) (0 27)
27 41 29 90
(0 18) (0 091)
41 23b 4124
(0 064) (0 082)
4155
(0 085) (0 063) (0 095)
4173 4181
3%
39 25
4140
EXP
4186 42 32 41 44b 4153 4194 42 12 42 15 42 81
(0 (0 (0 (0
20 9
25 2
05) 17) 093) 069)
(0 05) (0 24) (0 20) (0 056)
abash set (9s5p/4s) bTamm-Dancoff Green’s function results, relative mtensltles gwen m parentheses CAdlabatlc lomsatlon energies dRef 52, Ne(1) eMost Intense peak of vibrational progresslon Further references, He(I) angular dlstrlbutlon, refs 68, 69, synchrotron radlatlon, ref 44, photoelectron-photolon comcldence, ref 72, resonance electron capture, ref 24 Vznylfluonde
CZH3 F (C,) HAM/3
STO-3G
10 34
10a’
ii 9a’
+
(VP
.% 2a” (act )
ii E 5 E 8
la” (KF) 8a’ 70’ 6~’
GF*
EXP
8 30
10 43
10 63 (10 36)c’d
1530f 1330
(10 55)e
510
14 19
12 13
14 02
13 8
14 44
13 30
14 51
16 17 18 20
14 15 17 20
16 16 18 20 20
14 16 16 17 20
79 13 34 86
79 87 22 52
51 81 13 46b 96
(0 66) (0 18)
5 7 7 9 2
Vanylfluonde CzH3 F (C,) *
NJ)-’
3 5n’
(contmued)
HAM/3
STG-3G
24 76
26 60
GFa 24 34b
(0 053)
24 87
(0 040)
26 12
(0 50) (0 043)
26 26 4a’
39 66
4122
EXP
29 30
(0 081)
40 68b 4121
(0 072) (0 044)
4170
(0 042)
4172 4189
(0 053)
24 5
(0 25)
‘Bask set (Q&p/48) bTamm-Dancoff Green’s function results, relative mtensltles @ven m parentheses CAdlabatlc lonlsatlon energy dRefs 68, 69, He(I) angular dlstrlbutlon =Most intense p@ak of nbratlonal progrestuon ‘Ref 48, He(I) Further references He(I), refs 63, 74, photolonrsatlon, ref 64, photoelectron-photoion comcldence, ref 30, resonance electron capture, ref 24 Efhylfluorzde
C2 H5 F (C,)
+
(y7)-1
HAM/3
x
30”
12 12 12 61 14 07
12 4 12 9 14 0
E 2a” fi 80’ E lo”
14 11 16 01
14 5 16 0
F 7a’
17 60
a 6u’
2103
ii 1Oa’ E 9a’
ii
6cl’
24 33 37 38
17 1 210 (20 85)W 24 6
“Adlabatlc lonlsatlon energy b Ref 66 ‘This work Further references He(I), ref 76 3,3,3-l’kfiuoropropyne
CJ HF3 (G,)
5
w-’
HAM/3
EXP
2
6e @CC)
1166
12 (11 15 15
z la* ii 1Oq
15 27 15 37
1130b
17 1
17 33
4o’
EXP
1 96)“.b 3 3
1250’ 525
307
3,3,3-Trzfluompropyne +
C3 HF3
((23,) (contmued)
HAM/3
(P)-’
EXP
2; 5e
15 81
6
16 70
17 1
E 9a,
1804
184
F 3e
20 21
i? aa1
20 49
4e
ii
?a1
22 92
‘i
6q
25 72
2e
39 39
501
42 34
aAdlabahc
lomsatlon
lhfluorodmetylene
energy
15 9
20 6 -212 23 9 -25
bRef
8
9
C4 F2 (D_+,)
*
(VP
HAM/3
STO-3G
2
277,ehx-1
10 50
7 72
GFa
EXP
10 36
10 35 (10 05)“,d (10 33)=
2320& 1550 520 300
2
27L (Qc+)
12 71
1136
13 14
129 (12 sa,=*d
2290h 1450 520
4%
16 63
16 84
18 20
17 9
16 68
16 98
18 25
18 1
18 23
1792
19 76
19 3
19 64
18 91
20 87
2117
20 76
20 75b
(0 58)
23 99
26 11
2157 26 4ab
(0 53)
26 45
27 85
27 19 27 10b
40 26
43 56
28 10 42 21b
(0 08)
42 67
(0 10)
42 74
(0 35)
43 15
(0 15)
43 37 42 77b
(0 08)
42 83
(0 25)
43 57
(0 10)
40 28
43 56
20 7 216
(0 29) -24
3
(0 16) (0 13) (0 64)
(0 39)
abash set (9s5p) bTamm-Dancoff Green’s function results, relatwe mtenshes qven m parentheses =Adlabatx lonlaatlon energies dRef 10, He(I) =Most mtense peak of VP bratlonal progressIon f Ref 3, lonemuwon gflOcm_’ hRef 1 I
308 Perfluoropentadlyne-I,3
C5 F4 (CJ,)
J
G w’
HAM/3
EXP
2324
2
10 64
10 85 (10 58)&b
8e (rcc)
2280b” 1440 1140 880 710
21,22
A 7e (ncc)
12 77
20
ii la2
14 69
15 2
19
i? 16a1
15 2
17,18 15,16 13,14
5 6e j? 5e F 4e
15 04 15 24 16 11
12
G 15al
11
i;i 14q
9,lO ? 8 J
13 3 (13 09)Gb
15 17 18 19
16 35 18 17 19 50
3e (71~) 13q
340 1160b 760 340c
8 1 3 6
20 5
19 65 20 61
210 218
7
ii 12Ql
22 59
238
6 5
z
llq lOa,
24 64 26 52
25 2
3,4
2e
38 79
2
901
1
801
39 94 4175
aAdlabatlc lomsatlon energies bRef 3, lon-emlsslon c+1O cm-’ Further references He(I), ref 10 Hexafluorobenzene
Cd F6 (Deb ) HAM/3
--e (SCF)a
3233 X 2elg (ACC)
10 68
12 35
31
x
12 30
15 92
30
ii 2bzu
13 72
16 70
28,29
C 6e2g
14 74
17 70
27
5
1561 1581
19 20 19 41
1588 16 16
19 66 19 88
J
25,26 24 22,23
Q w-l
2%
(%x)h
lazs 6el, 1bZs
(TF)
le2”
@F)
EXP s
10 2 (9 906)12 8 (12 577)b” 140 (13 847)‘*’ 14 8 (14 760)b” 15 9 (16 2e
1516’ 1492c 1420’ 428
309
Hexafluorobenzene I
9
C6F6
(&h)
(d-l
(contrnued)
HAM/3
--E (SCF)a
Exp
17 23 18 18
20 74 20 83
17 6 (18 If
20,21
lelg
18,19
5e2s
17
%u
18 21
2189
15,16
5el,
18 48
2105
I 19 0)
14
5a1g
19 18
22 65
20 3
13
lb?,
19 39
12 10,ll
4blu
24 30(‘) 2187
20 3 20 3
4e2g
20 10 2145
4el,
25 32
26 31 3107
25 6
35 28
@F)
@F)
859 7
4a1,
29 04
6
3blu
38 98
495
3e2,
39 19
2,3
3eh
39 75
1
3alg
40 15
22 4
aRef 58, mmlmal-basis-set “ab mltlo” calculation bAdlabatlc lomsatlon energies ‘This work, high-resolution He(I) spectrum dIE, (2elJ1 = 9 90 eV, ref 73, He(I), IE, (2e,,)-’ = 9 91 eV, ref 69, He(I) angular dlstrlbutlon eBand-maxlmum at 16 5 eV fBand-maxlmum at 18 6 eV sRef 29, lon-enusslon, see also ref 12, laser-Induced fluorescence hOften referred at the g state (e g , refs 1,2, 32) Further references He(I), refs 7, 21, 33, 55, 74, He(II), refs 21,59, 61, Ion-emwon, refs 1, 2, 28, laser-Induced fluorescence, ref 12, in sohd matrix, ref 13, photolrphotoIon comcldence, refs 32, 35, resonance electron capture, ref 36, He(I) angular d&nbutlon, ref 47 Pentafluorobenzene
C6HF5
(C,,) HAM/3
I
+ w-’
30
if
29
2
28
E 4bl (GX)
12 21
27
E
13 57
26
5
3a2
(Tcc)
5bl hx)
13b2
10 29 10 61
Exp 99
(9 64)qb -10 1 12 7 (12 5o)“.b 13 9 (13 71y
25 24 23 22 21 20
14 16
20al i% 12b2
14 71
llbz 19a1 3bl
15 44 cnF)
2a2 tnF)
18al
15 15 15 16
58 74 91 32
P) 14 9 (14 79)qb (15 7d
e
310 Pentafluorobenzene 1
*
19 18 17 16 15
C6HF5
(confmued)
w-’
HAM/3
2bl (TF) la2 (AF) lob2
16 52 16 93 17 31
lb1
(773)
17q
14 13
(C,,)
Bxp
17 73 18 11
16q
18 11
9bz 15a,
18 79
1s: 7) 19 7
18 80
19 7
11
14q
19 60
10
8bz 13a1
20 96
20 1 22 0
12
9 8
7b2 12q
7
2106 24 83 24 86
6
lla,
5 4
lOal
28 57 38 77
3 2 1
6b2
38 90
9a1 562
39 46
801
39 78
22 0 25 0 25 0
39 21
*Adiabatic mmsatlon energlee bRef 73, He(I) ‘?hls work, He(I) (IE, = 13 82 eV, ref 73) dBand-maxlma at 15 8,16 2,16 5,17 6, and 18 3 eV eRef 29 Further references He(I), ref 55, lonemlsslon, refs 1, 2, laser-mduced fluorescence, ref 12, photon--photomn comcldence, refs 32,35, resonance electron capture, ref 36
1,2,3,4-Tetrafluorobenzene
C,jH2 F4 (C,,) HAM/3
1
3
27
2 402
26 25
2 4bl FCC) g 3bl WCC)
10 39 12 22
24 23 22 21
i? 16a, b 14b2 i% 15a* 13b2
13 13 14 15 15 15 15
W-’ WX)
10 10
Bxp 98
(9 6O)“.b
20 19 18
202 (nF)
17 16 15
2bl (‘IIF)
12b2 14al la2
13al
@F)
43 64 44 25 57 85 89
15 94 16 53 16 87
98 5 42)%’ 7 7 6 4d
12 (12 13 13 14 (15
1; 5)
e
311 1,2,3,4-Tetrafluorobenzene J
+
14 13
12 11 10 9 8 7 6 5 4 3 2 1
C&F4
(cp)-’
HAM/3
lb1 tnF) llbz 1201 lltll
17 36
(C,,)
1783 1832 1853 1904 2060 2063 2442 2442 2816 3859 3879 3913 3951
10bz
9bz lOa1 941
862 8a1 762 701 6bz 6~1
(contmued)
EXP 180 18 0 190 190 19 7 215 215 246 24 6
aAdlabatlc lonlsatlon enernes bRef 73, He(I) cRef 1, He(I)/lon-emuxnon dBandmaxuna at 15 5,16 1, and 17 2 eV =Ref 29 Further references He(I), ref 55, He(II), ref 59, lonemmuon, ref 2, pboton-photoion comcldence, ref 32,lasermduced fluorescence, ref 12 I, 2,3,5-Tetrafluoro J
*
benzene C!bHz F4 ( Czv )
(CPS’
HAM/3
EXP
27
2
26 25
2 2a2 okc) 2 461 @cc)
10
24 23 22 21 20 19 18 17 16 15 14 13 12 11
t? 12b2 fi 11b2 I 184~
13 37
13 6
1376 1445 1524 1557 1560 1617 1627 1630 1722 1737 1743 1811 1837
136 145 (155d
5bl (ncc)
lob2
9bz 3bl (KF) 1701 la2
@F)
2h
(ffF)
lb1
(TF)
1% ab2
7bz 15q
1007 44 1209
e 100 125 (1242)w
1' 0) 189 189
312 1,2,3,5-Tetrafluorobenzene I
C6H2F4 (C,,)
(conhued) Exp
HAM/3
Gzf w-’
10
14q
19 23
19 7
9
13al
20 59
211
8
6b2
20 63
216
7
5bz
24 41
24 7
6 5
12aI llal
24 42 28 13
24 7
4 3
lOa 9al
38 61 38 90
2
4bz
38 99
1
8al
39 41
aAdlabatlc lomsatlon ener@es bRef 73, He(I) CRef 1, He(I)/lon-emwslon dBandmaxnna at 15 5,16 0.16 5,17 3, and 17 7 eV eRef 29 Further references He(I), ref 55, He( II), ref 59,1on-emwlon, ref 2, photon-photoIon comcldence, ref 32, laser-induced fluorescence, ref 12 1,2,4,5-Tetrafluorobenzene 1
5
w-’
27
X 2blg (rcc)
C6H2F4 HAM/3 9 92
(D2h) Exp 95
(9 36)4b 10 2
26
A 2b3,(nx)
10 69
25
13 2b2, (ncc)
12 07
24 23
C 7&u
13 48 13 61
13 7 13 7 14 6 (15 4d
7hu
14 63 15 27 15 67 1588 16 02
8%
1611
22 21 20 19 18 17 16 15 14 13 12 11 10 9 8
5
9a,
E 6&g 8h.t %I lhg
tTF) (KF)
(10 04)“;b
4bzr
16 16 17 17 18 18 19 20
6%
20 60
14,
cTF)
W, lbzu 6h 5b3, 7% 6hu
(BF)
66 66 08 71 11 41 12 51
12 5 (12 35)“C
17 3) 17 9 17 9 18 9 18 9 19 5 210 216
e
313 1,2,4,5-Tetrafluorobenzene J
* 7
Cd H2 F4 (D2h) (contznued)
w’
HAM/3
4b3,
24 37
6
5bi,
24 43
5
5=g
28 11
4
3bzg
38 64
3
4bl,
38 69
2
3b3u
39 18
1
4%
39 26
Exp 24 8 24 a
aAdlabatlc lonlsatlon energies bRef 73, He(I) CRef 1, He(I)/lon-eml,won dBandmaxma at 15 5,15 7,16 1,16 4, and 17 0 eV eRef 29 Further references He(I), ref 55, He(U), ref 59, lon-emlsslon, ref 2, laser-Induced fluorescence, ref 12, photon-photolon comcldence, ref 32, resonance electron capture, ref 36 1,2,3-Trlftuorobenzene
(C,,)
HAM/3
J
$
24
z 4bl (WC)
23 22
C6H3F3
w-’
10 03
2
2a2 (~cc)
10 10
g
3h
12 20
(GX)
21
2
llb2
13 22
20
5 16~
19
i$ lob2
13 54 13 93
18
1521 1548
16
9bz 2bl (nF) 15al
15
14a1
16 01
17
14
la2
13
8b2
12 11
7b2
10 9 8
12al llal
7 6 5 4 3 2 1
lb1
(AF)
(nF)
13al
6b2 5b2 lOal gal 8=l 4b2 7=l
Exp
15 61 16 07 16 63 16 99 17 80
18 13 ia 41 20 20 20 20 24 01 24 04 27 38 38 39
17 2) 17 6
ia 4 ia 4 19 3 20 7 -20
7
24 24
76 46 80 23
Note added In proof aLaser-mduced fluorescence, V E Bondybey, J H Enghsh, T A Miller and R H Shlley, J Mol Spectrosc , 84 (1980) 124
314
1,2,4-Trzfluorobenzene C6H3 F3 (C,) w’
HAM/3
1
9
24
i 6a"(7rcc)
978
23 22
ii 5a"(Qc) ii 4a"(?lCc)
10 34
21 20 19 18 17 16 16 14 13 12 11 10 9 8 7 6 5 4 3 2 1
i? 27a' fi 26a’
1310 1340 1432 1531 1555 1560 1568 1609 1673 1691 1731 1806 1868 2015 2020 2400 2405 2772 3850 3869 3905
EXP 95
(9 3o)"'b 101 125 (12 3l)"'b 131 137 145 (154c
1206
E 25a’ 24a’ 23a’ 3a” (7t~) 22a’ 2a” (@) la” (?$)
21a' 20a' 19a’ 18a’
17a' 16a' 15a' 14a' 13a' 12a' lla' 100'
16 7) (17017 5) (179d18 6) 191 207 213 244 244
aAdlabatzc zonzsatlon energies bRef 1 cBand-maxmwm 18 1eV eRef 29 Further references
1,3,5-Trzfluorobenaene
lon-emlsslon, ref 2, photon-photolon
C&i3F3
--e (SCF)a
23,24 X 2e"(ncc)
1008
1114
22
1198
1511
1335 1373 1525
1601 1584 1817
5
w-’
at 16 0 eV dBand-maxlmum comcldence, refs 32, 35
(D3h) HAM/3
I
EXP 98 (9 64)b*c
ii 2aY (7rcc)
21 2 2ai 19,20 E 9e' 17,18 5 8e'
e
125 (1235)b" 13 6 136 154
e
at
316 1,3,5-TrQ7uorobenzene
C6H3 F3 (D3h) (contmued) HAM/3
--E (SCF)’
Exp
E le” (Q)
16 03
19 11
15 8
F la;’ (AF)
16 49
19 71
16 5
13
ii 7q E 7e’
19 79 19 45
17 0
11,12
16 82 17 10
10
7
1LT;
17 30
9
?
6a;
2150 2133
18 3 19 4
24 42
20 7d 21 3d 24 2
J
G w-’
15,16 14
7,8
6e’
18 88 20 16
5,6
5e’
24 00
29 28
4
5a;
27 68
33 33
4e’ 40;
38 73 38 81
2,3 1
17 3
aRef 58, mmunal-baslsset “ab mltlo” calculation bAdlabatlc lonlsatlon eneaes CRef 39, He(I) dBand-maxuna of Jahn-Teller durtorted 2E state (9) =Ref 29 Further references He(l), refs 33, 55, He(II), refs 59, 61, ion-em-on, refs 1, 2, laser-induced fluorescence, refs 12, 14, 15, 53 (also m sohd matnx, ref 15), resonance electron capture, ref 36, photon-photolon couwdence, ref 32 l,Z-Dzfluorobenzene
HAM/3
*
(P)‘-’
2
3h (ncc)
2
2a2
g
1341
13 77
16 28
(‘ITF)
15 21 15 35 15 50
(VF)
15 75 16 55
17 17 18 18 19 20 19
10bz
lllll
8bz 9al 8~1 7b,2 741 6bz
10 12 12 13
16 65 1762 17 19 19 23 23
90 67 79 63 68
Exp
10 52 10 86 14 58 14 97
9bz
lb1 lOa
9 74
--E (SCF)a
11 81 14 40
@cc)
E 2bl WCC) 5 11b2 I 12a1
la2
C6H4 F2 (C,,)
15 30
65 76 29 36 33 18 52
20 77 24 20 23 46
16 3) (16 ge li 18 20 20 23 23
9) 6 2 2 7 7
316 1,2-Lhfluorobenzene
C6 HqF2
(C,,)
HAM/3
@ w’
(contmued) --E (SCF)a
Exp
27 35
6~1
33 38
5bz 5a1
38 92
aRef 58, mmlmal-basis-set “ab mltio” calculation bAdlabatlc lomsatlon energies CRef 73 dBand maxma at 15 2,15 6, and 15 9 eV eBand maxuna at 17 1 and 17 6 eV Further references He(I), ref 55 1,3-Lhfiuorobenzene *
(cp)-’
2
202
(ncc)
x 3bl @cc) fi
2bl @cc)
E 14a1 5 lob2 ii? 9bz 13al 12Ul 142
(EF)
lb1
(TF)
8b2
lla1 lOi lOal gal 6bz
C6H4FZ (C,,) HAM/3 9 76 10 08 12 04
10 54
Exp 95
10 88
(9 32)b” 10 0
14 91
(9 68)’ 12 4
1295 13 35 13 68
14 73 15 33 16 48
1503 1544
(12 -12 13 -13
22)b.d 9 6 6
53 94 65 07 71 24
(14 8f I
16 31 16 54
17 17 18 19 18 19
16 92
20 33
17 7)
18 18 19 67 19 75
20 80
18 6 20 2
15 87 16 18
801
23 61 23 68
7a1 4bz 6al
27 31 38 59 38 63
5b2
--e (SCF)a
485e
1290e 970e
20 2 23 7 23 7
aRef 58, mmlmal-basis-set “ab mltlo” calculation bAdlabatlc lomsatlon energies ‘Ref 73, He(I) dRef 2, He(I)/lon-emlsslon e This work, high-resolution He(I) spectrum fBand-maxlma at 15 0,15 6,16 4,17 0, and 17 4 eV Further references He(I), ref 55, photon-photolon comcldence, ref 32
317
1,4-Dzfluorobenzene CgH4Fz (D2h) HAM/3
@ w-’
X %g @cc) A lh,
Okc)
B 4bzg
E 2bu
(ncc)
D 5b3,
E
8ag
%u 7blu 3bzg lb, (RF) lbu (nF)
Gp
--E(SCF)~
EXP 420f (9 14)e*f 1355f 101 (1003yvf 1450f 12 5 (1209)e*f 125 13 7 14 3 (14gg
9 50
937
10 39
1027
1002
1106
1249
1277
1433
1193 13 20 14 34 1507 1566 1500 1576 1595
12 61b" 1412 1438 1539 1581 1596 1681 17 87b" 1974 2020 1796
1645 1808 1730 19 59 19 58 2349
2b3,
2370
5%
2728
4blu
3797
4%
3798
1820 1873 2126b 2148 2213b 2258 2527b 2655 2683 2670b 2699 2711 2935b 3043 3055 3081 4131 427zb 4273 4287 4237b 4262 4271 4284
(0 76)
1488 1590 1642 1747 1791 1781 1864
(0 77) (0 070,o093) (0 064,O067) 2035
(0 24) (0 53) (0 54) (0 11) (0 15) (0 39) (0 18) (0 26) (0 17) (0 25) (0 05) (0 42) (0 11) (0 05) (0 95) (0 58) (0 19) (0 074)
1966 2075 2328
94
16 5) 805f 169 (1676)e*f 805f 172 (1713)"f 18 0 180 202
2431
-209
2854
239
2902
23 9
(005) (0 057) (047) (0 20) (contrnued
overleaf)
318 aBasls set (9s5p/4s), compare also ref 56 bTamm-Dancoff Green’s function results, relatwe intensities pven m parentheses ‘?I’he Green’s function IS non-diagonal in the lblu (q?) and 2bz,, (ffcc) orbltals This non-diagonal character fmds its major expresslon m the mtentnty-borrowmg mechsnlsm for the two satelhte hnes of largest relative mtensltles The two relative mtensltles which are given refer to the sunple hole-states 1 bzu and 2bzu In such a case, a statement about the mtensltles of a band can only be made d the dipole matrix elements are calculated This has not been done dRef 58, mmunal-baslsset “ab m&lo” calculation eAdlabatlc lomsatlon energies f This work, high-resolution He(I) spectrum sBand-maxlma at 15 16 and 15 5 eV Further references He(I), refs 33,55, 74, He(H), ref 59, resonance electron capture, ref 36 Fiuorobenzene
CgHsF HAM/3
+
w-’
2
3bl 6x)
2
la2
5
8bz
9 62
(C,,) --e (SCF)a 10 15
10 03 12 49
10 5
z 2bl @cc) 5 13Ul B 7bz
12 08 13 14 13 62
14 75 14 75 16 06
F 6b2 G 12q
14 91 16 26
17 08
ii 6bz
15 81 15 86 16 38
7
lb1 llal 1oq
(ncc)
(KF)
14 06
17 36 19 08 18 37 18 56
Exp 94 (9 22)b” 98 12 3 (11 79)b*d 12 3 13 13 (13 14 15 16
0 9 89)b*d 6 2 4
16 16 17 (17
4 4 7 67)b*d
17 37
20 30 23 65
%
19 20 19 24
8~1
23 2’7
22 85 28 14
23 3
3b2
23 43
28 50
23 3
27 04 37 97
32 22
4bz
7al 6~1
1370d 490d
19 7 19 7
aRef 58, mmlmal-bass-set “ab mltlo” calculation bAdiabatlc lomsatlon enewes CRef 69, He(I) angular dlstrlbutlon (ref 73, 9 19 eV) dThls work, high-resolution He(I) spectrum He(I), refs 31, 33, 55, 74, He(I) angular dlstrlbutlon, ref 67, Further references resonance electron capture, ref 36, ion photodlssoclatlon, ref 34
319 Hydrogen
fluorzde
HF (CL,)
6
w-’
HAM/3
lWPTa
GFb
z
In
16 81
16 16
1626
(0 94)
ii 30
19 80
19 73
72 29’ 20 Ogc
(0 038) (0 95)
(16 039)d*e 19 9
73 37
(0 030)
(19 118+”
ii 20
39 65
37 99’ 4097 43 00 10134
EXP
(0 (0 (0 (0
52) 35) 052) 031)
16 19
g h
39 6f
aRef 26 bBasls set [lls7pld/6slp] + (5s4pld/3slp) cTamm-Dancoff Green’s functlon results, basis set [9s5p/4s] + (4s2p/2s), relative mtensltxes gwen m parentheses dAdlabatlc lomsatlon energies eRef 40 threshold photoelectron spectrum ‘Ref 5, Mg KLY, Y Mt radlatlon %, = 3090 5 cm 4 , w&. = 89 cm-‘, ref 38 h~, = 1496 1 cm-‘, ueXe = 88 4 cm-‘, ref 38 Further references He(I), refs 8, 18, 50, 75, He(II), ref 18, 1on-emwslon, ref 38, (e,2e) ref 17, electron energy-loss spectroscopy, ref 65 Fluorme
Fz (D-h) HAM/3
RSPT’
GFb
EXP
i? 1 ng (TF-)
16 36
15 66
15 86
1587 (15 7O)d’”
i
19 40
18 69
18 99
20 40
20 80
2103
9
z
w-l
1% (w+) 3us
2; 20, i? 20,
36 36 42 43
1050e
18 8 21 If
28 87’
(0 11)
3617
(0 71)
40 53’ 4130
(0 56) (0 13)
56 19
(0 13)
aRef 25 bRef 57, basis set (lls7p2d) CTamm-Dancoff Green’s function results, relatwe mtenslttes given m parentheses dAdlabatlc lomsatlon energies =Ref 27 f Ref 11
Supplementary
References
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7
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43
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71 72 73 74 75 76
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ACKNOWLEDGEMENTS
This work has been supported by the SWISSNational Science Foundation (Part 135 of ProJect No 2 012-079, for Part 134, see ref 1) and by the
Swedish Natural Science Research Council One of us (G B ) would like to express his gratitude to the Swiss National Science Foundation for the grant of a fellowship. Financial support by Clba-Gelgy SA, F Hoffman-La Roche & Cle, Sandoz SA, and the Fonds der Deutschen Chemlschen Industne 1s gratefully acknowledged Finally we would like to thank Dr J P Maler and Mr P For&r (Umverslty of Basel) for the gft of some samples of fluoro-substrtuted benzenes, and Prof K. Slegbahn and Dr L Karlsson (Umverslty of Uppsala) for the probes of methyl fluonde and fluoroform. Last but not least we are obhged to Prof E Lmdholm (Stockholm) for thorough mspectlon of the manuscnpt
REFERENCES 1
2
3 4
5
6 7 8
W von Nlessen, G Btert and L kbrtnk, J Electron Spectrosc Relat Phenom , 21 (1980) 176 L &bnnk, C Fndh and E Ltndholm, Chem Phys Lett , 52 (1977) 63, 69, L Lbrmk, C Fndh, E Lmdholm, S de BrlliJn and D P Chong, Phys Scr , 22 (1980) 475 L S Cederbaum,Theor Chun Acta, 31(1973) 239, J Phys B, 8 (1975) 290 L S Cederbaum and W Domcke, Adv Chem Phys, 36 (1977) 205, J Schlrmer, Thesis, Techntcal Umverslty, Munich, 1977, J Schumer and L S Cederbaum, J Phys B, ll(l978) 1889 G BIerI, J P Stadehnann, F Thommen and J Vogt, Helv Chum Acta, 61 (1978) 367, G Bieri, Conf Proc , 4th Int Symp on Plasma Chemistry, 1979, Vol 2 (S Vepgek and J Hertz, Eds ), p 467 (Chem Abstr ,92 57952r) Houben-Weyl, Methoden der Organlschen Chemte (Halogensverbtndungen), Band V/3 (E Muller, Ed ), G Thteme Verlag, Stuttgart, 1962, pp 166,206 L M Denms, J M Veeder and E G Rochow, J Am Chem Sot ,53 (1931) 3263 C Cossart-Magos, D Cossart and S Leach, Mol Phys ,37 (1979) 793