VIBRONIC SPECTROSCOPY OF THE PHENYLCYANOMETHYL RADICAL 6/23/11 1 DEEPALI N. MEHTA, NATHANAEL M. KIDWELL, JOSEPH A. KORN, AND TIMOTHY S. ZWIER 66 th International.

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Presentation transcript:

VIBRONIC SPECTROSCOPY OF THE PHENYLCYANOMETHYL RADICAL 6/23/11 1 DEEPALI N. MEHTA, NATHANAEL M. KIDWELL, JOSEPH A. KORN, AND TIMOTHY S. ZWIER 66 th International Symposium on Molecular Spectroscopy RJ04 Department of Chemistry, Purdue University West Lafayette, IN 47907

Motivation 2 Titan is a model system for studies of primordial Earth 2 Titan’s chemistry occurs via ion and neutral pathways 2 Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules 3  long lifetimes  build up in concentration Nitrile and isonitrile RSRs could be especially important in the chemistry of Titan  complex nitrogen-containing compounds  aerosols (“tholins”) [1] Kemsley, J.,Chemical and Engineering News, 2007, 85, 11, Science, 2007, 316, [2] Raulin, F., Space Sci. Rev. 135, 2008, [3]Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130, Figure 1 1 : Schematic of reactions in Titan’s atmosphere.

Gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (PCM). Doubly resonance stabilized Motivation 3 PCM

Motivation 4 A comparison to the vibronic spectroscopy of 1- phenylpropargyl radical (1PPR) will be presented. PCM1PPR

Experimental 5 EXCITE Collisional cooling to zero- point vibrational levels Precursor sample D0D0 Cooling Supersonic Expansion benzyl cyanide phenylcyanomethyl radical Discharge Source Valve Face Ceramic Spacer Delrin Insulator Delrin Cap Electrode (-150V) Electrode (+550V)

Experimental 6 Laser Ports 2 Stage Ion Acceleration Einzel Lens Pulsed Valve MCP Time-of-Flight Tube Turning Prism Mass Gate Pulser Discharge Source 1C-R2PI Ionization continuum SnSn S0S0 2C-R2PI DnDn D0D0 Tuned Laser Method of Detection: Resonant 2 Photon Ionization (R2PI) followed by detection with a Time of Flight (TOF) mass spectrometer Tuned Laser Fixed Laser

2C-R2PI Phenylcyanomethyl (PCM) Radical (with tentative assignments) 7 a Time Dependent Density Functional Theory (DFT): B3LYP/6-311+G(d,p). Origin at 21,402cm -1. D 1 ( 2 A’’)  D 0 ( 2 A’’) transition a

2C-R2PI Comparison for PCM and 1PPR 8 Special thanks to the Timothy Schmidt group for providing the 1PPR excitation spectrum file! [3] Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130, [4] Neil J. Reilly; Masakazu Nakajima, Bligh A. Gibson, Timothy W. Schmidt, and Scott H. Kable; J. Chem. Phys, 2009, 130, PCM 1PPR

2C-R2PI Comparison for PCM and 1PPR 9 PCM 1PPR Special thanks to the Timothy Schmidt group for providing the 1PPR excitation spectrum file! [3] Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130, [4] Neil J. Reilly; Masakazu Nakajima, Bligh A. Gibson, Timothy W. Schmidt, and Scott H. Kable; J. Chem. Phys, 2009, 130,

Comparison of PCM and 1PPR Normal Modes 10 Comparison of Normal Modes in PCM and 1PPR PCM1PPR 3,4 Normal Mode Experimental (cm -1 ) Calculated a (cm -1 ) Normal Mode Experimental (cm -1 ) a Ground state frequencies were calculated using Density Functional Theory (DFT): B3LYP/6-311+G(d,p). Calculated frequencies were scaled by 0.90 to approximate the excited state geometry change. PCM PPR [3] Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130, [4] Neil J. Reilly; Masakazu Nakajima, Bligh A. Gibson, Timothy W. Schmidt, and Scott H. Kable; J. Chem. Phys, 2009, 130, “12” “6b” “6a”

Rotational Band Contours of Select Bands cm -1 Origin 2C-R2PI over vibronic band of interest Resolution is 0.08cm -1 c a b

Ionization Potential of Select Bands for PCM 12 D0D0 D1D1 Ion + e - Tuned Laser 201cm -1 Origin IP=7.935eV 1PPR IP=7.3eV 3 Fixed Laser [3] Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130,

13 Origin 201cm -1 Lifetime of Select Bands (at threshold IP) ∆ t (ns) Ion Signal

Summary 14 [3] Neil J. Reilly; Damian L. Kokkin; Masakazu Nakajima; Klaas Nauta; Scott H. Kable; Timothy W. Schmidt; J. Am. Chem. Soc. 2008, 130, [4] Neil J. Reilly; Masakazu Nakajima, Bligh A. Gibson, Timothy W. Schmidt, and Scott H. Kable; J. Chem. Phys, 2009, 130, PCM 1PPR PCM and 1PPR Comparison PropertyPCM1PPR 3,4 D 0 -D 1 origin (cm -1 )21,40221,007 Lifetime (ns) 455 ± Ionization Potential (eV)

Future Directions 15 Obtain Dispersed Fluorescence (DFL) spectra for PCM Pursue study of the phenylisocyanomethyl (PICM) radical  Excitation Spectrum  Lifetime  Ionization Potential  Resonant Ion Dip Infrared Spectroscopy PICM hνhν dischargebenzylisocyanide benzylcyanide

Acknowledgements 16 Professor Timothy S. Zwier The Zwier Group Josh Sebree (TB08, TD11) Evan Buchanan (WI10) Zachary Davis James Redwine Jacob Dean (RG11) Nathanael Kidwell (WI11) Joseph Korn Di Zhang Professor Timothy W. Schmidt (The University of Sydney)