Vibrational Spectroscopy and

Dynamics of HN3

Cassidy Houchins1, Dan Weidinger1, Doug Brown2 and Jeff Owrutsky1

1Chemistry Division, Naval Research Laboratory

2Department of Chemistry, US Naval Academy

This work supported by the Office of Naval Research

through the Naval Research Laboratory
 Outline

• Introduction
– Background and N3-
– Motivate acid studies
• Bulk Solvents
– Baseline for more complex systems
• Reverse Micelles
– One example of complex environment
• Conclusions
 Introduction

• Vibrational Energy Relaxation

– Depends on environment/phase –
solute/solvent interactions
• simple (gas)
• condensed (liquid)
• complex systems (confined,
interfaces)
• Small anions as benchmark probes
– Solvation in bulk (e.g. Li et al)
• VER correlates with frequency
• VER correlates with H-bonding
– Complex environments (e.g. Dahl et al)
• Confined heterogeneous
• Ionic liquids
• HN3 (Houchins et al)
– Do trends extend?
– New molecular probe?
Ohta, K.; Tominaga, K. Chem. Phys. Lett. 2006, 429, 136.
Li, M.; Owrutsky, J.; Sarisky, M.; Culver, J. P.; Yodh, A.; Hochstrasser, R. M. J. Chem. Phys. 1993, 98, 5499.
Dahl, K.; Sando, G. M.; Fox, D. M.; Sutto, T. E.; Owrutsky, J. C. J. Chem. Phys. 2005, 123, 084504.
Houchins, C.; Weidinger, D.W.; Owrutsky, J.C. J. Phys. Chem. B. 2010 (accepted for publication)
 FTIR of HN3 in CH2Cl2 and Toluene
FTIR of HN3 in CH2Cl2 and Toluene

 (NH str)  (N=N str)  (N-N str)

1 2 4

Absorbance (arb. units)

 (NH bend)
3

Toluene

CH2Cl2
3500 3000 2500 2000 1500 1000

Frequency (cm-1)
*Moore, C. B.; Rosengren, K. J.
v1 v2 v3 v4 v5 v6 Chem. Phys. 1966, 44, 4108.
Gas* 3336 2140 1264 1151 534 607
*Dows, D. A.; Pimentel, G. C. J.
CH2Cl2 3279.8 2136.2 -- 1158.2 -- -- Chem. Phys. 1955, 23, 1258.
Toluene 3248.3 2130.7 1267.4 1157.8 -- --
 FTIR of HN3 (ν2) and N3- (ν2)
in Several Solvents
HN3

Absorbance (OD)
H2 O
• Note axes!
Formamide

•
CH2Cl2
HN3 = small solvent shift
– Water different from other Toluene

solvents NMF

– Very little variation among 2200 2160 2120 2080

FA, CH2Cl2, Toluene, NMF
Frequency (cm-1)
-
N3

• N3- = large solvent shift H2 O

Absorbance (OD)
Formamide

NMF

CH2Cl2

Li, M.; Owrutsky, J.; Sarisky, M.; Culver, J. P.; Yodh, A.;
Hochstrasser, R. M. J. Chem. Phys. 1993, 98, 5499. Toluene

Dahl, K.; Sando, G. M.; Fox, D. M.; Sutto, T. E.; Owrutsky, J. C. J. 2080 2040 2000 1960
Chem. Phys. 2005, 123, 084504.
Frequency (cm-1)
 IR Pump – IR Probe for
Vibrational Energy Relaxation Times

HN3 N3-
• HN3 slower than N3 -
VER times, VER times,
T1 (ps) T1 (ps)
• Solvent trends extend from N3- H2O 2.3 0.8
to HN3 CH3OH 5.6 3.0
– VER scales with H-bonding Formamide 5.1 3.7
NMF 6.4 5.5
HN3 in bulk solvent
Toluene 8.1 5.2
Normalized Absorbance Change

CH2Cl2 20.5 7.4

CH2Cl2

Toluene

NMF

Formamide

0 10 20 30 40 50 60

Time (ps)
 Major results from bulk studies

Small range of δν
HN3 generally slower than N3-
N3-
Frequency Shift

Transient Abs.
HN3 HN3

N3-

Solvent
Time
VER and H-bonding scale
HN3 results promising…
N3-
K1 = 1/T1

How about more

HN3
complex environments?

Solvent
IR Spectroscopy of Solutes in Reverse Micelles

Reverse Micelles (RMs):

Surfactant stabilized water-in-oil dispersions
Water nanodroplets:
– monodisperse & controllable size
– radii increase with w=[water]/[surfactant]
few to tens of nm
Motivation: an
t
ct
– model interfacial system: biomimetic Surfa

– nanoparticle synthesis
– water confinement effects
Reverse Micelle (water in oil)

Spectroscopy of RMs:
– Standard characterization (TRFQ, IR of water): NP RMs
– IR of ions in RMs
Static IR – New diagnostic for RMs
Ultrafast – New venue for solute vibrational dynamics
 FTIR of HN3 (ν2) and N3- (ν1)
in Reverse Micelles

• Peaks shift in RMs of both surfactants…different from N3-

• Shoulders in AOT and NP suggests segregation
• HN3 peaks sensitive to
– Confinement
– Interface
HN3/N3- AOT RMs HN3/N3- NP RMs

N3- bulk HN3 bulk

HN3 bulk N3- bulk
Normalized Absorbance

Normalized Absorbance
w0=15 w0=14

w0=10 w0=9

w0=5 w0=4
HN3 N3-

2200 2150 2100 2050 2000 1950 2200 2150 2100 2050 2000 1950

Frequency (cm-1) Frequency (cm-1)

 VER of HN3 in RMs

• VER longer than in bulk…different from N3-

– 2.3 ps bulk vs. ~6 ps in AOT for all w0 studied
– 2.3 ps bulk vs. ~7 ps in NP for all w0 studied
• HN3 VER not sensitive to size suggests interface
• But sensitive to surfactant supports interface
Normalized Absorbance Change

Normalized Absorbance Change

AOT RMs NP RMs

w0=21 w0=14

w0=14 w0=9

w0=7 w0=4

Bulk
Bulk

-5 0 5 10 15 20 -5 0 5 10 15 20

Time (ps) Time (ps)

 Summary and Conclusions

VER and Spectra in Bulk

• Spectroscopically distinct from anion

• HN3 slower than N3- Other enviroments
• Small solvent-dependent shift • Anion exclusion
• Rate scales with solvent polymers
• Ionic liquids
• Acidic solvents

HN3 a new probe…in RMs

• VER and spectra shift from bulk for
both surfactants
• HN3 segregates into distinct regions of
RM
• Interrogates water/surfactant interface
 Acknowledgements

Coworkers :
National Research Council
Jeff Owrutsky
Office of Naval Research
Dan Weidinger
Doug Brown
Mike Pomfret
Dan Steinhurst
 IR Pump/Probe Spectroscopy

Two-color ultrafast (200 fs, 5 μJ) IR (~2000 cm-1) Energy Levels

•Broadband IR pump V=2
•Broadband IR frequency-resolved probe V=1
Vibrational
T1 by excited state (v=1→2) decay and (v=0→1) Energy
bleach recovery. V=0 Relaxation
(VER)

120 fs, kHz, Ti:Sapphire

OPA DFG
Regenerative Amplifier

polarizer

to lock-in amp, IR monochromator

computer detector
Sample
cell