Supplementary information for the Journal of Chemical Physics paper,
G3 and Density Functional Theory Investigations of the Structures and
Energies of SFnCl (n=0-5) and Their Anions
Jane M. Van Doren
Department of Chemistry, College of the Holy Cross, Worcester, Massachusetts,
01610-2395
Thomas M. Miller,§ and A. A. Viggiano
Space Vehicles Directorate, Air Force Research Laboratory, Hanscom Air Force
Base, Massachusetts 01731-3010
§
Also Institute for Scientific Research, Boston College
I. Density Functional Theory B3LYP/6-311+G(3df) geometries (Å units) for SFnCl
and SFnCl- (n = 1-5) in standard notation
SF5Cl (C4v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.587853
F
0.000000
F
-1.587853
0.000000
0.000000
0.000000
1.587853
0.000000
-1.587853
0.000000
-0.262438
1.818754
-1.844383
-0.281121
-0.281121
-0.281121
-0.281121
SF5Cl- (C4v, 2A1):
S
0.000000
Cl
0.000000
F
0.000000
F
1.686059
F
0.000000
F
-1.686059
0.000000
0.000000
1.686059
0.000000
-1.686059
0.000000
-0.340333
2.264715
-0.430119
-0.430119
-0.430119
-0.430119
SF4Cl (Cs, 2A’ ):
S
-0.329271
F
-0.369516
F
-1.915485
F
-0.369516
F
-0.369516
Cl
1.910861
-0.140589
1.413124
-0.336622
-0.150031
-0.150031
-0.278737
0.000000
0.000000
0.000000
1.636287
-1.636287
0.000000
SF4Cl (C4v, 2A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.638020
F
-1.638020
0.000000
0.000000
1.638020
-1.638020
0.000000
0.000000
-0.454874
1.577851
-0.542930
-0.542930
-0.542930
-0.542930
SF4Cl- (Cs, 1A’):
S
-0.466972
F
0.503360
F
-1.803676
F
-0.466972
F
-0.466972
Cl
1.622346
0.013581
1.269331
1.031088
0.141236
0.141236
-1.380195
0.000000
0.000000
0.000000
1.721053
-1.721053
0.000000
SF4Cl- (C4v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.755238
F
-1.755238
0.000000
0.000000
1.755238
-1.755238
0.000000
0.000000
-0.592536
1.556645
-0.471733
-0.471733
-0.471733
-0.471733
SF3Cl (Cs, 1A’ ):
S
0.575788
F
0.531284
F
0.531284
F
0.531284
Cl
-1.385722
-0.109907
-0.022416
1.467225
-0.022416
-0.649590
0.000000
1.682996
0.000000
-1.682996
0.000000
SF3Cl- (Cs, 2A’):
S
0.755986
F
0.755986
F
0.042654
F
0.755986
Cl
-1.534553
0.178299
0.276469
1.623584
0.276469
-1.320087
0.000000
1.746922
0.000000
-1.746922
0.000000
SF2Cl (C1, 2A):
S
-0.408363
Cl
1.743779
F
-1.998953
F
-0.568873
-0.279451
-0.146897
-0.504474
1.278748
0.242207
-0.093014
-0.235792
-0.019105
SF2Cl (Cs, 2A’):
S
0.671622
Cl
-1.343244
F
0.671622
F
0.671622
0.025050
0.117281
-0.133033
-0.133033
0.000000
0.000000
1.699147
-1.699147
SF2Cl- (Cs, 1A’):
S
0.000000
Cl
-1.237628
F
0.929292
F
1.408450
0.587455
-1.528001
2.101403
-0.259543
0.000000
0.000000
0.000000
0.000000
SF2Cl- (C2v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
0.000000
0.000000
1.845802
-1.845802
-0.699069
1.398972
-0.699857
-0.699857
SFCl (Cs, 1A’):
S
0.000000
F
1.580951
Cl
-0.836974
0.823211
0.450015
-1.013030
0.000000
0.000000
0.000000
SFCl- (Cs, 2A′):
S
0.000000
F
0.654277
Cl
-0.346382
0.610338
2.283080
-1.783126
0.000000
0.000000
0.000000
SCl (Cv, 2Π (state undetermined by computation)):
S
0.000000
0.000000
-1.027081
Cl
0.000000
0.000000
0.966664
SCl- (Cv, 1Sg ):
S
0.000000
Cl
0.000000
0.000000
0.000000
-1.099147
1.034491
II. MP2(Full)/6-31G(d) geometries (Å units) for SFnCl and SFnCl- (n = 1-5).
SF5Cl (C4v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.603741
F
0.000000
F
-1.603741
0.000000
0.000000
0.000000
1.603741
0.000000
-1.603741
0.000000
-0.252992
1.806149
-1.849680
-0.278043
-0.278043
-0.278043
-0.278043
SF5Cl- (C4v, 2A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.671170
F
0.000000
F
-1.671170
0.000000
0.000000
0.000000
1.671170
0.000000
-1.671170
0.000000
-0.328309
2.260275
-1.956343
-0.432351
-0.432351
-0.432351
-0.432351
SF4Cl (Cs, 2A’ ):
S
-0.302708
F
-0.343660
F
-1.908024
F
-0.343660
F
-0.343660
Cl
1.840846
-0.156061
1.420158
-0.312238
-0.158779
-0.158779
-0.271546
0.000000
0.000000
0.000000
1.635194
-1.635194
0.000000
SF4Cl (C4v, 2A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.635530
F
-1.635530
0.000000
0.000000
1.635530
-1.635530
0.000000
0.000000
-0.457059
1.561486
-0.534231
-0.534231
-0.534231
-0.534231
SF4Cl- (Cs, 1A’):
S
-0.495621
F
0.566442
F
-1.771361
F
-0.495621
F
-0.495621
Cl
1.629140
0.050218
1.245003
1.100778
0.205656
0.205656
-1.506902
0.000000
0.000000
0.000000
1.693335
-1.693335
0.000000
SF4Cl- (C4v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
F
1.702527
F
-1.702527
0.000000
0.000000
1.702527
-1.702527
0.000000
0.000000
-0.668468
1.589434
-0.453469
-0.453469
-0.453469
-0.453469
SF3Cl (Cs, 1A’ ):
S
0.579967
Cl
-1.340852
F
0.500556
F
0.500556
F
0.500556
-0.096035
-0.716516
1.498862
0.012643
0.012643
0.000000
0.000000
0.000000
1.672588
-1.672588
SF3Cl- (Cs, 2A’):
S
0.231809
Cl
-0.019549
F
-0.336081
F
-0.019549
F
-0.019549
0.481198
-2.101272
2.047067
0.533269
0.533269
0.000000
0.000000
0.000000
1.702660
-1.702660
SF2Cl (C1, 2A):
S
-0.401381
Cl
1.706870
F
-1.954371
F
-0.556152
-0.278869
-0.148682
-0.509425
1.286036
0.286058
-0.109391
-0.278134
-0.023788
SF2Cl (Cs, 2A’):
S
0.671615
F
0.671615
F
0.671615
Cl
-1.343230
0.118604
-0.219067
-0.219067
0.120326
0.000000
1.656984
-1.656984
0.000000
SF2Cl- (Cs, 1A’):
S
0.000000
F
1.803616
F
-1.803616
Cl
0.000000
0.727513
0.655837
0.655837
-1.379133
0.000000
0.000000
0.000000
0.000000
SF2Cl- (C2v , 1A1):
S
0.000000
Cl
0.000000
F
0.000000
F
0.000000
0.000000
0.000000
1.803616
-1.803616
-0.727513
1.379133
-0.655837
-0.655837
SFCl (Cs, 1A’):
S
0.000000
F
1.585285
Cl
-0.839269
0.827156
0.433053
-1.007764
0.000000
0.000000
0.000000
SFCl- (Cv, 2A1):
S
0.000000
F
0.000000
Cl
0.000000
0.000000
0.000000
0.000000
-0.693276
-2.411103
1.928962
SCl (Cv, 2Π (state undetermined in computation)):
S
0.000000
0.000000
-1.030764
Cl
0.000000
0.000000
0.970131
SCl- (Cv, 1Sg ):
S
0.000000
Cl
0.000000
0.000000
0.000000
-1.100387
1.035659
Vibrational frequencies (scaled by 0.989) for SFnCl optimized geometries and
frequency change upon attachment of an electron for density function theory
B3LYP/6-311+G(3df) optimized geometry.
Species
SF4Cl (Cs, 2A’)
Symmetry
A'
A'
A"
A'
A'
A"
A"
A'
A'
A"
A'
146
203
210
294
406
414
491
506
550
729
731
Anion/Neutral
Frequency Ratio
1.0
0.83
0.62
0.93
0.87
0.85
0.91
0.89
0.85
0.82
0.82
Frequency (cm-1)
SF4Cl (C4v, 2A1)
A1
A1
A1
B1
B2
B2
E
E
E
377
522
631
410
205
525
258
390
720
0.78
0.67
0.95
0.73
1.1
0.75
0.76
0.78
0.78
SF2Cl (C1, 2A)
A
A
A
A
A
A
160
238
341
402
592
795
1.3
0.68
0.65
0.83
0.81
0.90
SF2Cl (Cs, 2A’)
A'
A'
A"
A'
A'
A"
90
290
297
469
580
624
3.4
0.72
0.79
0.81
0.84
0.71
SCl
Sg
556
0.77