the first and second recoupled pair bonds in sulfoxy species tyler takeshita, d. e. woon, t. h....
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The First and Second Recoupled Pair Bonds in Sulfoxy Species
Tyler Takeshita, D. E. Woon, T. H. Dunning, Jr.
Department of ChemistryUniversity of Illinois at Urbana-Champaign
Outline
Recoupled pair bonding in SX, X=F, OH, OTrends in electron affinityImportance of pi bonding
Addition of F and O to SF (second recoupled pair bond)SF2 vs. FSOFuture work
Methodology
MRCI+Q and RCCSD(T)Correlation consistent basis sets aug-cc-pVXZ
X= T, QX = T+d, Q+d for S
Covalent and Recoupled Pair Bonds in SF
S S F F
FS S F
SF 4Σ-
SF 2Π
SF 4Σ-
SF 2Π
RCCSD(T)/AVQZD. E. Woon; T. H. Dunning, Jr; Molecular Physics; 107, 2009, p. 991
Covalent and Recoupled Pair Bonds in SF
S S F F
FS S F
4Σ- rSF : 1.882 Å2Π rSF: 1.601 Å
SF 4Σ-
SF 2Π
SF 4Σ-
SF 2Π
RCCSD(T)/AVQZD. E. Woon; T. H. Dunning, Jr; Molecular Physics; 107, 2009, p. 991
O SOS
SOH(4A’’)
S O S O
SO(3Π)
De: 12.3 kcal/molre: 1.571 Å
De: 12.4 kcal/molrSO: 1.975 ÅrOH: 0.970 Å
Recoupled Pair Bonds in SO, SOH
Effect of Electron Affinity
F S
De: 36.4 kcal/molre: 1.901 ÅF electron affinity: 3.40 eV
SF(4Σ-)
O S
De: 12.3 kcal/molre: 1.571 ÅO electron affinity: 1.46 eV
SO(3Π)
RCCSD(T)/AVQZ
Effect of Electron Affinity
F S
De: 36.4 kcal/molre: 1.901 ÅF electron affinity: 3.40 eV
SF(4Σ-)
O S
De: 12.3 kcal/molre: 1.571 ÅO electron affinity: 1.46 eV
SO(3Π)
RCCSD(T)/AVQZ
How important is pi bonding?
The Importance of Pi Bonding
F S
De: 36.4 kcal/molre: 1.901 ÅF electron affinity: 3.40 eV
SF(4Σ-)
O S
De: 12.3 kcal/molre: 1.571 ÅO electron affinity: 1.46 eV
SO(3Π)
RCCSD(T)/AVQZ
O S
De: 12.4 kcal/molrSO: 1.975 ÅrOH: 0.970 Å OH electron affinity: 1.53 eV
HSOH(4A’’)How important is pi bonding?
The Importance of Pi Bonding
F S
De: 36.4 kcal/molre: 1.901 ÅF electron affinity: 3.40 eV
SF(4Σ-)
O S
De: 12.3 kcal/molre: 1.571 ÅO electron affinity: 1.46 eV
SO(3Π)
RCCSD(T)/AVQZ
O S
De: 12.4 kcal/molrSO: 1.975 ÅrOH: 0.970 Å OH electron affinity: 1.53 eV
HSOH(4A’’)How important is pi bonding?Pi bonding reduces bond length.No significant difference in bond energy.
The Addition of F to SF
F
3A2
F S
F
S
F
3B1
S F
F S
4Σ-
S F
2Π
1A1
Re = 1.656 Åθ = 83.1°
Re = 1.666 Åθ = 162.7°
Re = 1.592 Åθ = 97.9°
D. E. Woon; T. H. Dunning, Jr; J. Phys, Chem; 113, 2009, p. 7915 RCCSD(T)/AVQZ
F
SF2 3A2
F S Re = 1.656 Å
θ = 83.1°
F
S
F
SF2 3B1
Re = 1.666 Åθ = 162.7°
S F
Re = 1.592 Åθ = 97.9°
SF2 1A1
S F
FSO 2A’’
O
F S O
FSO 2Π
RFS = 1.757 ÅRSO = 1.471 Åθ = 180°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108°
RCCSD(T)/AVQZ
RFS = 1.884 ÅRSO = 1.453 Åθ = 95.2°
F
S
O
FSO 2A’
D. E. Woon; T. H. Dunning, Jr; J. Phys, Chem; 113, 2009, p. 7915
F
SF2 3A2
F S Re = 1.656 Å
θ = 83.1°
F
S
F
SF2 3B1
Re = 1.666 Åθ = 162.7°
S F
Re = 1.592 Åθ = 97.9°
SF2 1A1
S F
FSO 2A’’
O
F S O
FSO 2Π
RFS = 1.757 ÅRSO = 1.471 Åθ = 180°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108°
RFS = 1.884 ÅRSO = 1.453 Åθ = 95.2°
F
S
O
FSO 2A’
D. E. Woon; T. H. Dunning, Jr; J. Phys, Chem; 113, 2009, p. 7915 RCCSD(T)/AVQZ
F
S
F
SF2 3B1
Re = 1.666 Åθ = 162.7°
F S O
FSO 2Π
RFS = 1.757 ÅRSO = 1.471 Åθ = 180°
Occ: 1.012
Occ: 1.999Occ: 0.591
Occ: 1.013Occ: 1.992
F
SF2 3A2
F S Re = 1.656 Å
θ = 83.1°
F
S
F
SF2 3B1
Re = 1.666 Åθ = 162.7°
S F
Re = 1.592 Åθ = 97.9°
SF2 1A1
S F
FSO 2A’’
O
F S O
FSO 2Π
RFS = 1.757 ÅRSO = 1.471 Åθ = 180°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108°
RFS = 1.884 ÅRSO = 1.453 Åθ = 95.2°
F
S
O
FSO 2A’
D. E. Woon; T. H. Dunning, Jr; J. Phys, Chem; 113, 2009, p. 7915 RCCSD(T)/AVQZ
F
SF2 3A2
F S Re = 1.656 Å
θ = 83.1°
F
S
F
SF2 3B1
Re = 1.666 Åθ = 162.7°
S F
Re = 1.592 Åθ = 97.9°
SF2 1A1
S F
FSO 2A’’
O
F S O
FSO 2Π
RFS = 1.757 ÅRSO = 1.471 Åθ = 180°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108°
RFS = 1.884 ÅRSO = 1.453 Åθ = 95.2°
F
S
O
FSO 2A’
D. E. Woon; T. H. Dunning, Jr; J. Phys, Chem; 113, 2009, p. 7915 RCCSD(T)/AVQZ
F
SF2 3A2
F S
Re = 1.656 Åθ = 83.1°
SF2 3A2 singly occupied antibonding orbital compresses bond angle in SF2
Occ: 1.027
Occ: 1.006
RFS = 1.884 ÅRSO = 1.453 Åθ = 95.2°
F
S O
FSO 2A’
Summary of Current Work
Comparison of SX; X=F, OH, O recoupled structuresElectron affinity predicts ligands recoupling abilityO and OH recoupled bonds follow trends in electron affinity
Addition of Oxygen to SF 4Σ- Linear structure with two recoupled pair bondsMore localized antibonding orbital in structure containing one recoupled pair bond.
Ongoing Work:Addition to SO 3Π and
Effect of Electron Affinity
F S O
FSO 2Π
H
S O
HSO
S F
FSO 2A’’
S O
HSO
Addition of H to SO 3Π is a covalent bondAddition of F to SO 3Π is a second recoupled pair bond
RHS = 1.346 ÅRSO = 1.658 Åθ = 93.0°
RHS = 1.369 ÅRSO = 1.488 Åθ = 105.0°
RFS = 1.757 ÅRSO = 1.471 Åθ = 180.0°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108.0°
O
RCCSD(T)/AVQZ
Ongoing Work:Addition to SO 3Π and
Effect of Electron Affinity
F S O
FSO 2Π
H
S O
HSO
S F
FSO 2A’’
S O
HSO
Addition of H to SO 3Π is a covalent bondAddition of F to SO 3Π is a second recoupled pair bondEffect of electron affinity?
RHS = 1.346 ÅRSO = 1.658 Åθ = 93.0°
RHS = 1.369 ÅRSO = 1.488 Åθ = 105.0°
RFS = 1.757 ÅRSO = 1.471 Åθ = 180.0°
RFS = 1.606 ÅRSO = 1.454 Åθ = 108.0°
O
RCCSD(T)/AVQZ
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