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Proton Sponges A Simple Organic Motif for Revealing the Quantum Structure of
the Intramolecular Proton Bond
H+ H+
H+
H+
H+
H+
H+
H+
H+
H+
H+H+
H+
H+N N
H3CH3C CH3
CH3
N N
H3CH3C CH3
CH3H
Andrew F DeBlase Christopher M Leavitt Timothy L Guasco Michael T Scerba Thomas Lectka and Mark A Johnson
June 23 2011
Ohio State University International Ohio State University International Symposium on Molecular SpectroscopySymposium on Molecular Spectroscopy
Ar
Pre
dis
soci
atio
n Y
ield
The Shared ProtonThe Shared ProtonShared proton vibrational frequency well characterized by vibrational predissociation spectroscopy
Roscioli et al Science 2007
1000 1500 2000 2500 3000 3500
Photon Energy (cm-1)
Stoyanov and Reed J Phys Chem A 2006
Ab
sorp
tio
n
O H+
OCH2CH3
CH2CH3
CH3CH2
CH3CH2
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
- Imidazole wires for anhydrous membranes
+
N N
C C
C
N N
C C
C
N N
C C
C
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
Gerardi et al J Chem Phys Lett 2011
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
bull Proposed increase in binding affinity of pharmaceuticals
- Neutral H-bond 15-fold increase
- Charged H-bond 3000-fold increase
N H F R N H C R
R
R
F
bull Enhancement of organic bases (proton sponges)
- Destabilized base
- Stabilized conjugate acid intramolecular proton bond
N N
H3CH3C CH3
CH3H
N N
H3CH3C CH3
CH3H
H+ldquoSmeared outrdquo QM particle
N N
H3CH3C CH3
CH3
1 8
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Ar
Pre
dis
soci
atio
n Y
ield
The Shared ProtonThe Shared ProtonShared proton vibrational frequency well characterized by vibrational predissociation spectroscopy
Roscioli et al Science 2007
1000 1500 2000 2500 3000 3500
Photon Energy (cm-1)
Stoyanov and Reed J Phys Chem A 2006
Ab
sorp
tio
n
O H+
OCH2CH3
CH2CH3
CH3CH2
CH3CH2
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
- Imidazole wires for anhydrous membranes
+
N N
C C
C
N N
C C
C
N N
C C
C
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
Gerardi et al J Chem Phys Lett 2011
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
bull Proposed increase in binding affinity of pharmaceuticals
- Neutral H-bond 15-fold increase
- Charged H-bond 3000-fold increase
N H F R N H C R
R
R
F
bull Enhancement of organic bases (proton sponges)
- Destabilized base
- Stabilized conjugate acid intramolecular proton bond
N N
H3CH3C CH3
CH3H
N N
H3CH3C CH3
CH3H
H+ldquoSmeared outrdquo QM particle
N N
H3CH3C CH3
CH3
1 8
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
- Imidazole wires for anhydrous membranes
+
N N
C C
C
N N
C C
C
N N
C C
C
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
Gerardi et al J Chem Phys Lett 2011
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
bull Proposed increase in binding affinity of pharmaceuticals
- Neutral H-bond 15-fold increase
- Charged H-bond 3000-fold increase
N H F R N H C R
R
R
F
bull Enhancement of organic bases (proton sponges)
- Destabilized base
- Stabilized conjugate acid intramolecular proton bond
N N
H3CH3C CH3
CH3H
N N
H3CH3C CH3
CH3H
H+ldquoSmeared outrdquo QM particle
N N
H3CH3C CH3
CH3
1 8
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
Gerardi et al J Chem Phys Lett 2011
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
bull Proposed increase in binding affinity of pharmaceuticals
- Neutral H-bond 15-fold increase
- Charged H-bond 3000-fold increase
N H F R N H C R
R
R
F
bull Enhancement of organic bases (proton sponges)
- Destabilized base
- Stabilized conjugate acid intramolecular proton bond
N N
H3CH3C CH3
CH3H
N N
H3CH3C CH3
CH3H
H+ldquoSmeared outrdquo QM particle
N N
H3CH3C CH3
CH3
1 8
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Applications of Shared Proton BondsApplications of Shared Proton Bondsbull Fuel Cell Membranes
bull Proposed increase in binding affinity of pharmaceuticals
- Neutral H-bond 15-fold increase
- Charged H-bond 3000-fold increase
N H F R N H C R
R
R
F
bull Enhancement of organic bases (proton sponges)
- Destabilized base
- Stabilized conjugate acid intramolecular proton bond
N N
H3CH3C CH3
CH3H
N N
H3CH3C CH3
CH3H
H+ldquoSmeared outrdquo QM particle
N N
H3CH3C CH3
CH3
1 8
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
What to ExpectWhat to Expect
ldquoUniversal Trendrdquo For intermolecular A∙H+∙B Gas Phase Dimers
Letrsquos start in easiest range to measureLetrsquos start in easiest range to measure
FN
Roscioli et al Science 2007
PA[(CH3)3N] = 9391 kJmol-1
PA[CH3F] = 6318 kJmol-1
Parrillo et Al J Am Chem Soc 1993
Beauchamp Annu Rev Phys Chem 1971
∆PA = 3073 kJmol-1
asymp 3200 cm-1
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Experimental SetupExperimental Setup
Ion optics
ElectrosprayNeedle
RF Only Quadrupoles
Octopoles
Pressure (Torr)
3D Quadrupole Ion Trap with Temperature Control to 8 K
TOF to IR Spectrometer
New Cryogenic Ion Source
3times10-7 1times10-5 15times10-2 15 760
HeatedCapillary
90deg Ion Bender
Wiley-McLarenExtraction Region
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
2600 2700 2800 2900 3000 3100 3200 3300 3400 3500 3600
Photon Energy (cm-1)
Loss D2
Loss 2H2
NH3CH3C H
NH3CH3C
FH
CndashHStretches
NndashH+∙∙∙FStretch
Predissociation
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)
Free
D2 CndashHStretches
NndashH+
stretch
ResultsResults ldquoThe Lone Rangerrdquo
ExpD2
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
600 800 1000 1200 1400 1600 2600 2800 3000 3200 3400
Photon Energy (cm-1)
Ca
lcu
late
d In
ten
sity
Pre
diss
oci
atio
n Y
ield
NH3 CH3C
FH
NndashH+∙∙∙FStretch
MP26-311+G(NH Scaled 0943)(CH Scaled 0957)(BendingDeformations 0977)
Loss 2H2Loss D2
CH and NHBending
ResultsResults
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
MP2aug-cc-pVTZ
N N
Minimal energy PT path(1)N-N contraction(2)Ammonium N-H elongation
Asmis et al Angew Chem Int Ed 2007
AnharmonicitiesN-H 464 cm-1 calcN-H + N-N = 743 cm-1
N-H + 2N-N = 1069 cm-1
N-H + 3N-N = 1440 cm-1
Potential Energy SurfacesPotential Energy Surfaces
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Potential Energy SurfacesPotential Energy Surfaces
N
H
H
H
N
H
HH
H
r
y
x
R
y = 0
x = 0Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
R (
Aring)
y (Aring
)
x (Aring)
N N
H3CH3C CH3
CH3HR
x (Aring)
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
04 06 08 10 12 14 16 18 20 22-20
0
20
40
60
80
100
120
V(x
) (k
cal∙m
ol-1)
x (Aring)
R1 R2
H+
R1 = (CH3)2N R2 = F
R1 = (CH3)2N R2 = OH
x
y
R1 = R2 = (CH3)2N
Potential Energy SurfacesPotential Energy Surfaces
∆E1larr0797 cm-1
2744 cm-1
2897 cm-1
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Future WorkFuture Workbull Get spectra
- Compounds in the fridge
- Others being synthesized
Substitution
R1 R2
N(CH3)2 N(CH3)2
N(CH3)2OH
N(CH3)2OMe
N(CH3)2OEt
NH2OH
NH2OMe
NH2OEt
N(CH3)2 OCF3
NH2 OCF3
bull Question When will shared proton couple
to aromatic vibrations
bull Use motiffs that increasedecrease
proton donor-acceptor distance
eg R1 R2
H+
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
AcknowledgementsAcknowledgementsbull Labmates Especially Tim Guasco and Chris Leavittbull Mark New science new hobbiesbull Tom Lectkarsquos group at JHU for making the moleculesbull Funding National Science Foundation Air Force
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Supplemental SlidesSupplemental Slides
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Potential Energy SurfacesPotential Energy Surfaces
U(r
) (k
cal∙m
ol-1)
r(N-H) Aring
R = 300 Aring
R = 287 Aring
R = 275 Aring
R = 250 Aring
EquilibriumR asymp 275 Aring R = 275 Aring
N
H
H
H
N
H
HH
H
r
y
x
R Jaroszewski Lesyng Tanner McCammon Chem Phys Lett 1990
Image fromFoces-Foces et alJ Mol Struct 1990
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition
Deviation from Universal TrendDeviation from Universal Trend
Breaks down if ∆PA is small and ∆μ is large
Gardenier Roscioli and Johnson J Phys Chem A 2008
PA = 882 kJmol = 205 D
Photon Energy (cm-1)
800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600800 1200 1600 2000 2400 2800 3200 3600
x20x20x20x20
Predicted Shared-Proton
Transition