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)
Recoupled Pair Bonds in SO, SOH
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
Recoupled Pair Bonding Predictions for SF + O
F S
4Σ-
S F
2Π
S F
2A’’
O
F S
OFSO 2A’
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
Acknowledgements
Thom H. Dunning, Jr. Dr. David E. Woon, Dr. Lina Chen, Jeff Leiding, Beth Lindquist, Lu Xu.
Support for this work was provided by funding from the Distinguished Chair for Research Excellence in Chemistry at the University of Illinois at Urbana-Champaign.