Vibronic Spectroscopy of Jet-Cooled 1,4- Phenylene Diisocyanide 6/21/11 1 DEEPALI N. MEHTA , ANNA K. GUTBERLET, AND TIMOTHY S. ZWIER 66 th International Symposium on Molecular Spectroscopy TG07 Department of Chemistry, Purdue University West Lafayette, IN 47907
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Vibronic Spectroscopy of Jet-Cooled 1,4-Phenylene Diisocyanide 6/21/11 1 DEEPALI N. MEHTA, ANNA K. GUTBERLET, AND TIMOTHY S. ZWIER 66 th International.
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Vibronic Spectroscopy of Jet-Cooled 1,4-Phenylene Diisocyanide
6/21/11 1
DEEPALI N. MEHTA, ANNA K. GUTBERLET, AND TIMOTHY S. ZWIER
66th International Symposium on Molecular SpectroscopyTG07
Department of Chemistry, Purdue UniversityWest Lafayette, IN 47907
Motivation
2
[1] Kemsley, J. ,Chemical and Engineering News, 2007, 85, 11[2] Raulin, F., Space Sci. Rev. 135, 2008, 37-48
Figure 11: Schematic of reactions in Titan’s atmosphere.
• Titan is a model system for studies of primordial Earth2
• Titan’s chemistry occurs via ion and neutral pathways. 2
• The formation of benzene (78 amu) has been investigated.3
• Compounds at 78 amu and greater, suggesting possibility benzene-based derivatives.4
Motivation
3
[3] Wilson, E. H., and Atreya, S. K., J. Geophys. Res.-Planet, 2004, 109[4] J. H. Waite, D. T. Young, T. E. Cravens, A. J. Coates, F. J. Crary, B. Magee, J. Westlake, Science, 2007, 316, 870-875
Figure 24: Density as a function of mass, for compounds present in Titan’s atmosphere. Note the presence of mass 128.
128 amu
Motivation
4
• Species such as HCN, HC3N, C2N2, and NH3 open up possibility of nitrogen containing benzene derivatives.5
• Interest in isocyanides (also called isonitriles) which contain the R-N≡C group.
• Spectroscopy of isonitriles is less well understood• 1,4-phenylene diisocyanide (1,4-
PDI, Figure 3) shares the same (nominal) mass as naphthalene (128 amu), and is an interesting candidate for spectroscopic investigation
Figure 3: Structure of 1,4 phenylene diisocyanide[5] A. J. Trevitt, G. Boulay, C. A. Taatjes, D. L. Osborn, S. R. Leone, J. Phys. Chem. A, 2010, 114, 1749-1755
+ -+-C CNN
Motivation
5
34,255cm-1
35,120cm-1
865cm-1
[6] J. A. Stearns, T. S. Zwier, J. Phys. Chem. A, 2003, 10717-10724[7] K. Fujita, T. Fujiwara, K. Matsunaga, F. Ono, A. Nakajima, H. Watanabe, T. Koguchi, I. Suzuka, H. Matsuzawa, S. Iwata, K. Kaya, J. Phys. Chem., 1992, 96, 10693-10697.
?
para-Diethynylbenzene
para-Dicyanobenzene
1,4-Phenylene Diisocyanide
N NC C
C CN N
C CHC CH
Experimental
6
Collisional cooling to zero-point vibrational levels
Sample entrained in high pressure backing gas
Supersonic Expansion
S0
Cooling
Laser Induced Fluorescence
UV
lase
r (tu
ned)
(S0,v=0)
A*(Sn)Detect total
fluorescence
PMT
UV
lase
r (fix
ed)
Total
fluorescence
CCD
Dispersed Fluorescence
Experimental
7
LaserPorts
2 Stage IonAcceleration
Einzel Lens
Pulsed Valve
MCP
Time-of-Flight Tube
Mass Gate Pulser
1C-R2PI
Ionization continuum
Sn
S0
2C-R2PI
Sn
S0
Resonant 2 Photon Ionization (R2PI)
Tuned Laser
Fixed Laser
Tuned Laser
Experimental
8
UV-UV Holeburning
S0
Sn
20 Hz Probe(Tuned)
10 HzHB
Δt = 200 ns
Ionization continuum
Δt = 50-200 ns
HoleburnLaser (10Hz)
ProbeLaser (20Hz)
Spectra collected using active baseline subtraction
Wavenumbers (cm-1)
Probe only
Difference
*
Probe + Holeburn
Lasers spatially overlapped but temporally separated
2.5
2.0
1.5
1.0
0.5
0.0
Inte
nsi
ty
4000039000380003700036000Wavenumbers (cm
-1)
35,566
36,024(rel=458)
*
*
*
*
LIF Spectrum of 1,4-Phenylene Diisocyanide (PDI)
9
Origin at 35,566cm-1
S0-S1 LIF excitation spectrum, spanning 35,000-40,500cm-1. The S0-S1 electronic origin of 1,4-PDI has been identified as 35,566cm-1. Peaks marked * were anticipated to be due to other species.
Dispersed fluorescence of S0-S1 electronic origin at 35,566cm-1.
-3000 -2000 -1000 0Relative Wavenumbers (cm
-1)
Dispersed fluorescence of vibronically coupled mode 17 at 36,024cm-1. Inset within the graph is a visualization of normal mode 17, which has b3g symmetry.
ν17
1711
Δv=0171
0
Δv=-1171
2
Δv=+1
Dispersed Fluorescence of +458cm-1 Band
12
Vibronic Coupling and Tentative Assignments
13
Table 2. Experimental Calculated Symmetryν3 1671 1679 ag
ν5 1204 1215 ag
ν6 823 842 ag
ν7 393 396 ag
ν11 403 414 b2g
ν12 187 182 b2g
ν15 1327 1347 b3g
ν16 649 662 b3g
ν17 500 508 b3g
ν35 305 303 b3u
ν36 83 84 b3u
Calculated frequencies provided as courtesy of Head-Gordon group, using Qchem with rimp2-cc-pvdz .
Table 1. Symmetry Oscillator Strength
S1 B2u 0.0015
S2 B1u 0.6065
Excited state calculations using time dependent density functional theory were performed using Gaussian 09 with a b3lyp functional and 6-31+g(d) basis set
B2u × b3g=B1u
2.5
2.0
1.5
1.0
0.5
0.0
Inte
nsi
ty
4000039000380003700036000Wavenumbers (cm
-1)
35,566
36,024(rel=458)
*
*
*
*
LIF Spectrum of 1,4-Phenylene Diisocyanide (PDI)
14
Origin at 35,566cm-1
S0-S1 LIF excitation spectrum, spanning 35,000-40,500cm-1. The S0-S1 electronic origin of 1,4-PDI has been identified as 35,566cm-1.
1710
000
Identification of S0-S2
15
S0-S2 LIF excitation spectrum, spanning 40,500-44,100cm-1, approximately 6,100cm-1 above the S0-S1 origin.
Dispersed fluorescence of S0-S2 at 41,711 cm-1. The broadened emission near the S0-S1 origin suggests a S2S1 internal conversion, followed by fluorescence to the ground state.
S0
S1
S2
Internal Conversion
Discussion: Comparison of Isoelectronic Species
17
865cm-1
34,255cm-1
35,120cm-1
para-Diethynylbenzene
para-Dicyanobenzene
[6] J. A. Stearns, T. S. Zwier, J. Phys. Chem. A, 2003, 10717-10724[7] K. Fujita, T. Fujiwara, K. Matsunaga, F. Ono, A. Nakajima, H. Watanabe, T. Koguchi, I. Suzuka, H. Matsuzawa, S. Iwata, K. Kaya, J. Phys. Chem., 1992, 96, 10693-10697.