Higher Electronic Excited States of Jet-Cooled Aromatic Hydrocarbon Radicals: 1-phenylpropargyl (C9H7), 1-naphthylmethyl (C11H9), 2-naphthylmethyl (C11H9)

Slides:



Advertisements
Similar presentations
CYCLOPROPYLACETYLENE STUDIED IN COLD FREE JET EXPANSION, ROOM TEMPERATURE GAS, AND DILUTE SOLUTION: TIER MODEL IVR PAM L. CRUM, GORDON G. BROWN, KEVIN.
Advertisements

Rotationally-resolved infrared spectroscopy of the polycyclic aromatic hydrocarbon pyrene (C 16 H 10 ) using a quantum cascade laser- based cavity ringdown.
Frequency and Time Domain Studies of Toluene Adrian M. Gardner, Alistair M. Green, Julia A. Davies, Katharine L. Reid and Timothy G. Wright.
Spectroscopy The Light Spectrum. Vibrational Spectroscopy D(t) r(t) Band structure The higher the BO: i) the deeper the Well, ii) the wider the spacing.
D.L. KOKKIN, N.J. REILLY, J.A. JOESTER, M. NAKAJIMA, K. NAUTA, S.H. KABLE and T.W. SCHMIDT Direct Observation of the c State of C 2 School of Chemistry,
Electronic Spectroscopy of 1-Methylpyrene cation and related species. D. Kokkin, C. Marshall, A. Bonnamy, And C. Joblin and A. Simon.
Felix Güthe 1, Hongbin Ding, Thomas Pino 3, Tim W. Schmidt 4, Andrei Boguslavskiy John Maier Institut für Physikalische Chemie der Universität Basel, Basel,
Electronic Spectroscopy of long Carbon Chains HC 2n H (n= 8-13) in the Gas Phase Felix Güthe*, Hongbin Ding, Thomas Pino and John P. Maier Institut für.
Diagnosis of a benzene discharge with a mass-selective spectroscopic technique Felix Güthe, Hongbin Ding, Thomas Pino and John P. Maier Institute of Physical.
Felix Güthe 1, Hongbin Ding, Thomas Pino 3, Tim W. Schmidt 4, Andrei Boguslavskiy John Maier Institut für Physikalische Chemie der Universität Basel, Basel,
Chapter 12 Infrared Spectroscopy and Mass Spectrometry
La-Mediated Bond Activation, Coupling, and Cyclization of 1,3-butadiene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry.
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.
Infrared spectroscopy of Li(methylamine) n (NH 3 ) m clusters Nitika Bhalla, Luigi Varriale, Nicola Tonge and Andrew Ellis Department of Chemistry University.
Copyright © Professor Sang Kuk Lee, Department of Chemistry, Pusan National University. All rights reserved. 1 The 67 th International Symposium on Molecular.
Spectroscop1c Analysis Part 6 – Spectroscopic Analysis using Fluorescence and Atomic Absorption Spectrophotometry Chulalongkorn University, Bangkok, Thailand.
Anion Photoelectron Spectroscopic Studies of NbC 4 H 4 ‾, NbC 6 H 6 ‾ and NbC 6 H 4 ‾ Products of Flow Tube Reactions of Niobium with Butadiene Melissa.
Aloke Das Indian Institute of Science Education and Research, Pune Mimicking trimeric interactions in the aromatic side chains of the proteins: A gas phase.
68th International Symposium on Molecular Spectroscopy Ohio State University June 17-21, 2013 Wei-Li Li, Tian Jian, Gary V. Lopez, and Lai-Sheng Wang Department.
Laboratory of Molecular Spectroscopy & Nano Materials, Pusan National University, Republic of Korea Spectroscopic Identification of New Aromatic Molecular.
High-resolution threshold photoionization and photoelectron spectroscopy of propene and 2-butyne Julie M. Michaud, Konstantina Vasilatou and Frédéric Merkt.
Modeling Linear Molecules as Carriers of the 5797 and 6614 Å Diffuse Interstellar Bands Jane Huang, Takeshi Oka 69 th International Symposium on Molecular.
Integral field spectroscopy of the Red Rectangle: Unraveling the carrier of the RRBs in 2D. Damian Kokkin, Robert Sharp, Masakazu Nakajima, and Timothy.
Manifestation of Nonadiabatic Effects in the IR Spectrum of para-Benzoquinone Radical Cation Krzysztof Piech, Thomas Bally Department of Chemistry, University.
Pulsed-jet discharge matrix isolation and computational study of Bromine atom complexes: Br---BrXCH 2 (X=H,Cl,Br) OSU 66 th International Symposium on.
Created with MindGenius Business 2005® Mass Spectrometry Mass Spectrometry.
Electronic Spectroscopy of Palladium Dimer (Pd 2 ) 68th OSU International Symposium on Molecular Spectroscopy Yue Qian, Y. W. Ng and A. S-C. Cheung Department.
Electronic Transitions of Palladium Monoboride and Platinum Monoboride Y.W. Ng, H.F. Pang, Y. S. Wong, Yue Qian, and A. S-C. Cheung Department of Chemistry.
SPECTROSCOPY OF AND PHOTOINDUCED ELECTRON TRANSFER IN THE COMPLEXES OF C 2 H 4 WITH I AND I 2 Lisa George, Aimable Kalume, and Scott A. Reid Department.
Cavity Ringdown Spectroscopy of the A 2 A 2 - B 2 B 2 Vibronically Mixed Excited States of the Benzyl Radical and the 1 2 A 2 ← X 2 B 1 Transition of the.
Jet-Cooled Spectroscopy of 1- Naphthylmethyl, 2-Naphthylmethyl & Acenaphthenyl Radicals Nahid Chalyavi.
Interrogating hydrocarbon radicals
Laboratory of Molecular Spectroscopy, Pusan National University, Pusan, Republic of Korea Spectroscopic identification of isomeric trimethylbenzyl radicals.
IDENTIFYING FLUORESCENT HYDROCARBON RADICALS FROM A BENZENE DISCHARGE. Neil J. Reilly, Damian L. Kokkin, Scott H. Kable & Timothy W. Schmidt (Not)
Theoretical Study on Vibronic Interactions and Photophysics of Low-lying Excited Electronic States of Polycyclic Aromatic Hydrocarbons S. Nagaprasad Reddy.
Mass Spectroscopy Introduction.
Copyright © Professor Sang Kuk Lee, Department of Chemistry, Pusan National University. All rights reserved. 1 The 67 th International Symposium on Molecular.
IR spectra of Methanol Clusters (CH3OH)n Studied by IR Depletion and VUV Ionization Technique with TOF Mass Spectrometer Department of Applied Chemistry.
Suman K. Pal, Patrick Z. El-Khoury, Andrey S.
12. Structure Determination: Mass Spectrometry and Infrared Spectroscopy Based on McMurry’s Organic Chemistry, 6 th edition.
Infrared Resonance Enhanced Photodissociation (IR- REPD) Spectroscopy used to determine solvation and structure of Ni + (C 6 H 6 ) n and Ni + (C 6 H 6.
California State University, Monterey Bay CHEM312
Photochemical and Discharge-driven pathways to aromatics from 1,3-butadiene: Exploring aromatic production in Titan’s atmosphere. Josh J. Newby, Jaime.
Triplet-Singlet Mixing in Si­ 3 : the 1 A A 2 Transition Ruohan Zhang and Timothy C. Steimle International Symposium on Molecular Spectroscopy 68.
Structure in the Visible Absorption Bands of Jet-Cooled Phenyl Peroxy Radicals Michael N. Sullivan *, Keith Freel, J. Park, M.C. Lin, and Michael C. Heaven.
Main Title Manori Perera 1 and Ricardo Metz University of Massachusetts Amherst 64 th International Symposium on Molecular Spectroscopy June 25th, 2009.
Itaru KURUSU, Reona YAGI, Yasutoshi KASAHARA, Haruki ISHIKAWA Department of Chemistry, School of Science, Kitasato University ULTRAVIOLET AND INFRARED.
Spectroscopic investigation of temperature effects on the hydration structure of phenol cluster cation Reona YAGI, Yasutoshi KASAHARA, Haruki ISHIKAWA.
Photoelectron spectroscopy of the cyclopentadienide anion: Analysis of the Jahn- Teller effects in the cyclopentadienyl radical Takatoshi Ichino, Adam.
Tyler P. Troy, Scott H. Kable, Timothy W. Schmidt Department of Chemistry, University of Sydney Scott A. Reid Department of Chemistry, Marquette University.
Spectroscopic and Theoretical Determination of Accurate CH/  Interaction Energies in Benzene-Hydrocarbon Clusters Asuka Fujii, Hiromasa Hayashi, Jae Woo.
Ce-Promoted Bond Activation of Ethylene Probed by Mass-Analyzed Threshold Ionization Spectroscopy Department of Chemistry University of Kentucky, Lexington,
* Funded by NSF. Xiujuan Zhuang and Timothy C. Steimle* Department of Chemistry and Biochemistry Arizona State University, Tempe,AZ Neil Reilly,
The 70 th International Symposium on Molecular Spectroscopy, TH07, June 23, The 70 th Meeting of International Symposium on Molecular Spectroscopy,
Laser spectroscopy of a halocarbocation: CH 2 I + Chong Tao, Calvin Mukarakate, and Scott A. Reid Department of Chemistry, Marquette University 61 st International.
High-resolution IR absorption spectroscopy of Polycyclic Aromatic Hydrocarbons (PAHs): shining light on the interstellar 3 micron emission bands… Elena.
CONFORMATION-SPECIFIC ELECTRONIC SPECTROSCOPY OF JET-COOLED 5-PHENYL-1-PENTENE NATHAN R. PILLSBURY, TALITHA M. SELBY, AND TIMOTHY S. ZWIER, Department.
SPECTRA OF JET-COOLED ALL- BENZENOID PAHS - TRIPHENYLENE (C 18 H 12 ) AND HEXA-PERI- HEXABENZOCORONENE(C 42 H 18 ) DAMIAN L. KOKKIN, TYLER P. TROY, NEIL.
Theodore P. Snow Nicholas Betts Meredith Drosback Veronica Bierbaum
The exotic excited state behavior of 3-phenyl-2-propynenitrile
Mitsunori ARAKI, Hiromichi WAKO, Kei NIWAYAMA and Koichi TSUKIYAMA○
UV Spectroscopy of 3-phenyl-2-propynenitrile
Mass-Analyzed Threshold Ionization Spectroscopy
Metastable States Arising from the Ablation of Solid Copper
Tokyo Univ. Science Mitsunori Araki, Yuki Matsushita, Koichi Tsukiyama
Thomas D. Varberg, Department of Chemistry, Macalester College, St
from W. Demtröder “Molecular Physics”
T. L. Guasco, B. M. Elliott, M. Z. Kamrath and M. A. Johnson
from W. Demtröder “Molecular Physics”
Tryptophan - gas phase tautomer
Presentation transcript:

Higher Electronic Excited States of Jet-Cooled Aromatic Hydrocarbon Radicals: 1-phenylpropargyl (C9H7), 1-naphthylmethyl (C11H9), 2-naphthylmethyl (C11H9) and 9-anthracenylmethyl (C15H11) The University of Sydney School of Chemistry Gerard Dean O’Connor Klaas Nauta and Timothy W. Schmidt Molecular Photonics Group | UNSW

The Diffuse Interstellar Bands (DIBs) StarInterstellar MediumEarth

What are the carriers of the DIBs? Amorphous CarbonFullerenesCarbon Chains & Carbenes Polycyclic Aromatic Hydrocarbons (PAHs) H2CnH2Cn

Testing the PAH hypothesis: gas phase spectroscopy Resonantly stabilized radicals and their cations ultraviolet spectra visible spectra ultraviolet spectra h h visible spectra

Reilly, N.J; Kokkin, D.L; Masakazu N; Klaas N; Kable, S.H and Schmidt, T.W. (2008). "Spectroscopic Observation of the Resonance-Stabilized 1-Phenylpropargyl Radical J. Am. Chem. Soc DOI: /ja078342t Chalyavi, N; Troy, T.P; Nakajima, M; Gibson, B.A; Nauta, K; Sharp, R.G; Kable, S.H and Schmidt, T.W. (2011) “Excitation and emission spectra of jet-cooled naphthylmethyl radicals.” J. Phys. Chem A, 115 (27), , DOI: /jp203638h O’Connor, G.D; Bacskay, G.B; Woodhouse, G.V.G; Troy T.P; Nauta, K; Schmidt, T.W. (2013) “Excitation Spectra of Large Jet-Cooled Polycyclic Aromatic Hydrocarbon Radicals: 9-Anthracenylmethyl (C15H11) and 1-Pyrenylmethyl (C17H11)” The Journal of Physical Chemistry A,117(50) DOI: /jp D 1 ← D 0 excitation spectra of jet cooled aromatic radicals in the gas phase

Trends in Larger Resonance Stabilised Radicals 6 D 1 ← D 0 transitions weak (oscillator strength f~10 -4 ) Larger molecules D 1 ← D 0 spectra non-origin dominated

1-PyMe R2C2PI Excitation Spectrum cm -1

Assigned 1-PyMe Excitation Spectrum, low frequency modes 8 80% intensity of origin

9 D0D0 D1D1 DnDn Transition Moments John A. Pople H.C. Longuet-Higgins Longuet-Higgins, H.; Pople, J. Proc. Phys. Soc. Lond. A 1955, 68, 591–600 f~10 -4 f >10 -2

Detector Source Extraction of ions Time-Of- Flight MS Resonant 2-Colour 2-Photon Ionization (R2C2PI) Ionisation continuum  +e - 

Detector Source Extraction of ions Time-Of- Flight MS Double Resonant Depleation Ionisation continuum d +e - D0D0 D1D1 D3D3

1-phenylpropargyl calculated transitions 12 CASPT2 [6311G(d)] electrons in 9 orbital active space D 3 ← D 0 Vertical excitation energy = cm -1 Oscillator Strength = G.V.G. Woodhouse: Undergraduate Honours Thesis, 2012

D 3 ← D 0 excitation spectrum of 1-phenylpropargyl radical 13 FWHM=149 cm -1 Lifetime = 36 fs Too high in energy to be a DIB

Matrix results of the naphthylmethyl radicals D 1 ← D 0 1&2-npme Nagy, Fulara, and Maier. J. Am. Chem. Soc. 2011, 133, 19796– Calculated (by us) to be weak (CASPT2 and TD-B3LYP) We calculate both to be strong (CASPT2 and TD-B3LYP) and assign both to D 3 ← D 0 D 2 ← D 0 2-npme D 3 ← D 0 1&2-npme

D 3 ← D 0 excitation spectra of naphthylmethyl radicals 15 FWHM=290 cm -1 FWHM=292 cm -1 Lifetime = 18 fs Broadest DIB FWHM = 155 cm -1

Ionisation lifetime scan of 9-anthracenylmethyl 16

eV photon energy similar to IE

18 Signal independent of lifetime

Trends in TD-B3LYP vertical excitation energy 19 Benzyl data from: : Porter, G; Wright, FJ; (1955) “PRIMARY PHOTOCHEMICAL PROCESSES IN AROMATIC MOLECULES.3. ABSORPTION SPECTRA OF BENZYL, ANILINO, PHENOXY AND RELATED FREE RADICALS” TRANSACTIONS OF THE FARADAY SOCIETY 51 (11)

9-AnMe Vertical Excitation Energies B3LYP/TD-DFT G(d,p) 20 B3LYP TD-DFT [6311++G(d,p)] (corrected) – 23874(cm -1 ) M06 TD-DFT [6311++G(d,p)] (corrected) – 24229(cm -1 )

D 3 ← D 0 excitation spectrum of 9-anthracenylmethyl radical 21 FWHM=326 cm -1 Lifetime = 16 fs

Trends in TD-B3LYP vertical excitation energy 22

Trend, the energy gap law in action 23

Trends in observed in polycyclic aromatic hydrocarbon resonance stabilised radicals (PAH RSRs) 24 odd-alternate hydrocarbon radicals D 1 ← D 0 extremely weak (f ≈10 -4 ), with most intensity going to higher energy transition transitions with intensity greater than f ≈10 -2 have been calculated and observed Strong visible transitions of PAH RSRs will be significantly broader then any observed DIBs As these are the transitions most likely to be observed, PAH RSR can be largely dismissed as potential DIB carriers

Acknowledgements 25 Supervisor: Prof Tim Schmidt Co-Workers: Gabrielle Woodhouse Prof Scott Kable Dr Klaas Nauta Dr Tyler Troy Laser Spectroscopy Group UNSW Molecular photonics group

Feedback: Privacy Policy Feedback
Do Not Sell My Personal Information
About project: SlidePlayer Terms of Service

© 2024 SlidePlayer.com. Inc. All rights reserved.