The Rotational Spectrum of the Water–Hydroperoxy Radical (H 2 O–HO 2 ) Complex Kohsuke Suma, Yoshihiro Sumiyoshi, and Yasuki Endo Department of Basic Science,

Slides:

Advertisements

Similar presentations

“Rotational Energy Transfer in o - / p -H 2 + HD” Renat A. Sultanov and Dennis Guster BCRL, St. Cloud State University St. Cloud, MN June 20, 2007 OSU.

Advertisements

1 THz vibration-rotation-tunneling (VRT) spectroscopy of the water (D 2 O) 3 trimer : --- the 2.94THz torsional band L. K. Takahashi, W. Lin, E. Lee, F.

Spectra, Structures, and Dynamics of Weakly Bound Clusters from Dimers to Nonamers Wolfgang Jäger Department of Chemistry, University of Alberta.

OXYGEN-18 STUDIES OF HOCO AND HONO FORMATION Oscar Martinez Jr. and Michael C. McCarthy Harvard-Smithsonian Center for Astrophysics School of Engineering.

Millimeter-wave Spectroscopy of the Tunneling-rotation Transitions of the D 2 CCD radical M. Ohtsuki, M. Hayashi, K. Harada, K. Tanaka Department of Chemistry,

Infrared Spectroscopy of Doubly-Charged Metal-Water Complexes

High-Resolution Spectroscopic Studies of Reaction Intermediates relevant to Atmospheric Chemistry Yasuki Endo Department of Basic Science The University.

Galen Sedo, Jamie L. Doran, Shenghai Wu, Kenneth R. Leopold Department of Chemistry, University of Minnesota A Microwave Determination of the Barrier to.

Rotational Spectra of Methylene Cyclobutane and Argon-Methylene Cyclobutane Wei Lin, Jovan Gayle Wallace Pringle, Stewart E. Novick Department of Chemistry.

DENNIS J. CLOUTHIER, ROBERT GRIMMINGER, and BING JIN, Department of Chemistry, University.

Ab Initio Calculations of the Ground Electronic States of the C 3 Ar and C 3 Ne Complexes Yi-Ren Chen, Yi-Jen Wang, and Yen-Chu Hsu Institute of Atomic.

The Study of Noble Gas – Noble Metal Halide Interactions: Fourier Transform Microwave Spectroscopy of XeCuCl Julie M. Michaud and Michael C. L. Gerry University.

Observation of the weakly bound (HCl) 2 H 2 O cluster by chirped-pulse FTMW spectroscopy Zbigniew Kisiel, a Alberto Lesarri, b Justin Neill, c Matt Muckle,

Microwave Spectrum of Hydrogen Bonded Hexafluoroisopropanol  water Complex Abhishek Shahi Prof. E. Arunan Group Department of Inorganic and Physical.

Zeinab. T. Dehghani, A. Mizoguchi, H. Kanamori Department of Physics, Tokyo Institute of Technology Millimeter-Wave Spectroscopy of S 2 Cl 2 : A Candidate.

Microwave Spectra and Structures of H 2 S-CuCl and H 2 O-CuCl Nicholas R. Walker, Felicity J. Roberts, Susanna L. Stephens, David Wheatley, Anthony C.

The effective Hamiltonian for the ground state of 207 Pb 19 F and the fine structure spectrum Trevor J. Sears Brookhaven National Laboratory and Stony.

Physique des Lasers, Atomes et Molécules

Rotational Spectra and Structure of Phenylacetylene-Water Complex and Phenylacetylene-H 2 S (preliminary) Mausumi Goswami, L. Narasimhan, S. T. Manju and.

Electronic Spectroscopy of DHPH Revisited: Potential Energy Surfaces along Different Low Frequency Coordinates Leonardo Alvarez-Valtierra and David W.

Microwave Spectrum and Molecular Structure of the Argon-(E )-1-Chloro-1,2-Difluoroethylene Complex Mark D. Marshall, Helen O. Leung, Hannah Tandon, Joseph.

Bonding & dynamics of CN-Rg and C 2 -Rg complexes Jiande Han, Udo Schnupf, Dana Philen Millard Alexander (U of Md)

Rotationally-Resolved Spectroscopy of the Bending Modes of Deuterated Water Dimer JACOB T. STEWART AND BENJAMIN J. MCCALL DEPARTMENT OF CHEMISTRY, UNIVERSITY.

Rotational spectroscopy of oxygen bearing radicals and radical complexes Yasuki Endo 2006/June/19 The University of Tokyo.

61st OSU International Symposium on Molecular Spectroscopy RI12 Rotational spectrum, electric dipole moment and structure of salicyl aldehyde Zbigniew.

Equilibrium Molecular Structure and Spectroscopic Parameters of Methyl Carbamate J. Demaison, A. G. Császár, V. Szalay, I. Kleiner, H. Møllendal.

Fourier transform microwave spectra of CO–dimethyl sulfide and CO–ethylene sulfide Akinori Sato, Yoshiyuki Kawashima and Eizi Hirota * The Graduate University.

Int. Symp. Molecular Spectroscopy Ohio State Univ., 2005 The Ground State Four Dimensional Morphed Potentials of HBr and HI Dimers Collaborator: J. W.

Ab Initio and Experimental Studies of the E Internal Rotor State of He-CH 3 F Kelly J. Higgins, Zhenhong Yu, and William Klemperer, Department of Chemistry.

Effective C 2v Symmetry in the Dimethyl Ether–Acetylene Dimer Sean A. Peebles, Josh J. Newby, Michal M. Serafin, and Rebecca A. Peebles Department of Chemistry,

Millimeter-Wave Spectroscopy of the vdW Bands of He- HCN the Dissociation Limit. Millimeter-Wave Spectroscopy of the vdW Bands of He- HCN Above the Dissociation.

K. Iwakuni, H. Sera, M. Abe, and H. Sasada Department of Physics, faculty of Science and Technology, Keio University, Japan 1 70 th. International Symposium.

Perfluorobutyric acid and its monohydrate: a chirped pulse and cavity based Fourier transform microwave spectroscopic study Javix Thomas a, Agapito Serrato.

The Ohio State University International Symposium on Molecular Spectroscopy 68th Meeting - - June 17-21, 2013 Microwave Spectrum of Hexafluoroisopropanol,

Mohammed Gharaibeh, Fumie X. Sunahori, and Dennis J. Clouthier Department of Chemistry, University of Kentucky Riccardo Tarroni Dipartimento di Chimica.

0 ipc kiel The rotational spectrum of the pyrrole-ammonia complex Heinrich Mäder, Christian Rensing and Friedrich Temps Institut für Physikalische Chemie.

Intermolecular Interactions between Formaldehyde and Dimethyl Ether and between Formaldehyde and Dimethyl Sulfide in the Complex, Investigated by Fourier.

The rotational spectra of helium- pyridine and hydrogen molecule- pyridine clusters Chakree Tanjaroon and Wolfgang Jäger.

N 2 -CO 2 Consequences for Global Warming? Daniel Frohman Wesleyan University TH01 June 22, 2010.

Photoelectron spectroscopy of the cyclopentadienide anion: Analysis of the Jahn- Teller effects in the cyclopentadienyl radical Takatoshi Ichino, Adam.

Infrared Spectra of Anionic Coinage Metal-Water Complexes J. Mathias Weber JILA and Department of Chemistry and Biochemistry University of Colorado at.

Rotational Spectroscopic Investigations Of CH 4 ---H 2 S Complex Aiswarya Lakshmi P. and E. Arunan Inorganic and Physical Chemistry Indian Institute of.

Microwave Spectroscopy and Internal Dynamics of the Ne-NO 2 Van der Waals Complex Brian J. Howard, George Economides and Lee Dyer Department of Chemistry,

Photoelectron Spectroscopy of Pyrazolide Anion Three Low-lying Electronic States of the Pyrazolyl Radical Adam J. Gianola Takatoshi Ichino W. Carl Lineberger.

Observation of the pure rotational spectra of trans and cis-HOCO Takahiro Oyama, Yoshihiro Sumiyoshi, Yasuki Endo Department of Basic Science, The University.

Biman Bandyopadhyay, Prasenjit Pandey, Amit K. Samanta, Anamika Mukhopadhyay, Tapas Chakraborty Association Complexes of 1,3-Cyclohexanedione: Probing.

Helen O. Leung, Mark D. Marshall & Joseph P. Messenger Department of Chemistry Amherst College Supported by the National Science Foundation.

Microwave Spectroscopic Investigations of the Xe-H 2 O and Xe-(H 2 O) 2 van der Waals Complexes Qing Wen and Wolfgang Jäger Department of Chemistry, University.

Spectroscopic and Ab Initio Studies of the Open-Shell Xe-O 2 van der Waals Complex Qing Wen and Wolfgang Jäger Department of Chemistry, University of Alberta,

The gerade Rydberg states of molecular hydrogen Daniel Sprecher, 1 Christian Jungen, 2 and Frédéric Merkt 1 1 Laboratory of Physical Chemistry, ETH Zurich,

The 61 th International Symposium on Molecular Spectroscopy. ‘06 Funded by: NSF- Exp. Phys. Chem Mag. Hyperfine Interaction in 171 YbF and 173 YbF Timothy.

Rotational Spectra of N 2 O-H 2 Complexes University of Alberta Jen Nicole Landry and Wolfgang Jäger June 23, 2005.

Fourier-transform microwave spectroscopy of the CCCCl radical Takashi Yoshikawa, Yoshihiro Sumiyoshi, and Yasuki Endo Graduate School of Arts and Sciences,

LASER INDUCED FLUORESCENCE SPECTROSCOPY OF THE SiNSi RADICAL II: IDENTIFICATIONS OF THE A2A1, B2B1, AND D2Sg+ STATES C. MOTOYOSHI, Y. SUMIYOSHI, Y. ENDO.

Rotational spectra of C2D4-H2S, C2D4-D2S, C2D4-HDS and 13CH2CH2-H2S complexes: Molecular symmetry group analysis Mausumi Goswami and E. Arunan Inorganic.

1Kanagawa Institute of Technology 3Georgia Southern University

Carlos Cabezas and Yasuki Endo

Jacob T. Stewart and Bradley M

M. Rezaei, J. George, L. Welbanks, and N. Moazzen-Ahmadi

3-Dimensional Intermolecular Potential Energy Surface of Ar-SH(2Pi)

FT Microwave and MMW Spectroscopy of the H2-DCN Molecular Complex

Becca Mackenzie Chris Dewberry, Ken Leopold

The Three-dimensional Potential Energy

Fourier transform microwave spectra of n-butanol and isobutanol

BROADBAND MICROWAVE SPECTROSCOPY AS A TOOL TO STUDY DISPERSION INTERACTIONS IN CAMPHOR-ALCOHOL SYSTEMS MARIYAM FATIMA, CRISTÓBAL PÉREZ, MELANIE SCHNELL,

Wei Lin, Anan Wu, Zin Lu, Daniel A. Obenchain, Stewart E. Novick

F H F O Semiexperimental structure of the non rigid BF2OH molecule (difluoroboric acid) by combining high resolution infrared spectroscopy and ab initio.

and analysis of hyperfine structure from four quadrupolar nuclei

THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE Nazir D. Khan, Helen.

Presentation transcript:

The Rotational Spectrum of the Water–Hydroperoxy Radical (H 2 O–HO 2 ) Complex Kohsuke Suma, Yoshihiro Sumiyoshi, and Yasuki Endo Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo

Background Free radical processes of atmospheric species in troposphere HO 2 and OH play central role in atmosphere Their water complexes should play important roles by changing the reactivities of radical monomers.

Chaperon effect HO 2 + HO 2 → H 2 O 2 + O 2 Recombination of HO 2 Sink of atmospheric HO 2 Source of atmospheric H 2 O 2 HO 2 + HO 2 → H 2 O 2 + O 2 (1) HO 2 + H 2 O ⇄ HO 2 –H 2 O(2) HO 2 + HO 2 –H 2 O → products(3) HO 2 –H 2 O + HO 2 –H 2 O → products(4) Complex formation of H 2 O–HO 2 † k Water enhances this reaction † E. Hamilton Jr., R. Lii, Int. J. Chem. Kinet 9, 875 (1977).

Experiment Water + O 2 (10 %) / Ar H 2 O–HO kV 4.5 atm Unlike the case of Ar–HO 2 Suma et al, JCP Pulsed discharge Production of H 2 O–HO 2 Observation FTMW Spectroscopy Double Resonance Spectroscopy

Equilibrium geometry by ab initio calculation RCCSD(T)/aug-cc-pVTZ

Internal rotation Intermolecular potential energy surface /cm –1 B3LYP/aug-cc-pVDZ TS1 E E* Barrier (TS1) 200 cm –1

Internal rotation TS2 E (12)* Barrier (TS2) 200 cm –1 Intermolecular potential energy surface /cm –1 B3LYP/aug-cc-pVDZ

The group G 4 Index table of the group G 4 E(12)E*(12)* A A – 1 1–1–1 B – 1–1–1 1 B + 1–1 1–1 A–A– B + / B – C1C1 G4G4 B + / B –  ortho (A + ) = B + / B –  nuc  total A +  para (B + ) = B +  vib

Observed spectra Coupling scheme of angular momenta A + state B + / B – state J = 2.5 – signals 370 signals I 1 ： H nucleus of HO 2 I 2 ： H nuclei of water I 1 = ½ I 2 = 0 para (A + ) = 1 ortho (B + / B – ) F 1 = J + I 1 F = F 1 + I 2

Stick diagram A + B + / B –

Energy levels and observed transitions FTMW Double resonance a-typeb-type A B + / B – Observed lines Same rotational transitions were observed for the A + and B + / B – state.

Molecular constants A + (para)B ± (ortho) A (7) (5) B (4) (3) C (3) (3) Δ N (1) (6) Δ NK 0.021(1)0.0816(8) Δ K (Fix) (Fix) δ N (1)0.0062(1) δ K (Fix) (Fix) ε aa –557.23(3)–553.69(2) ε bb –409.99(2)–409.76(1) ε cc –0.91(2)–0.98(1) |ε ab + ε ba |/ (5)154.68(4) Δ N S (6)0.0031(4) Δ NK S 0.050(6)0.060(4) HO 2 side a F –27.51(2)–27.49(9) T aa 28.49(1)28.51(1) T bb –17.58(2)–17.59(2) T ab –11.8(2)–11.6(1) Water side a F ––0.040(6) T aa –4.870(7) T bb ––2.384(9) T ab –1.11(9) in MHz Hyperfine constants σ=11 kHz (A + ) =12 kHz (B + / B – ) A + (para)B ± (ortho)

Molecular structure ab initio Experiment r e TS1 TS2 A + B + / B – A /MHz B /MHz C /MHz ΔI / uÅ 2 – –2.337–0.092–0.229 Inertial defects: small negative values →Vibrationally averaged structure is nearly planar. →Large amplitude motion Large deviation (5%) Rotational constants Ab initio (r e ) Experiment

RCCSD(T)/aug-cc-pVTZ Features Hydorgen bond （ R O1 － H3 ） is short. -cf. water dimer Å Non-linear hydrogen bond O2 － H3 ･･･ O1 (ab initio Å) Molecular structure ←experimental (B+C)

Binding energy Exp ab initio* Δ N 37.5(1) 39.5 δ N 6.4(1)6.2 Centrifugal distortion constants (kHz) *B3LYP/aug-cc-pVTZ The ab initio PES reproduces the centrifugal distortion constants well. →supports the accuracy of D e. Binding energy (D e kcal/mol) H 2 O–H 2 O5.0 † H 2 O–OH5.6 † † H 2 O–HO † † † † W. Klopper et al. PCCP. 2, 2227 (2000). † † Aloisio et al. Acc. Chem. Res. 33, 825, (2000) † † † This work (RCCSD(T)/aug-cc-pVTZ)

Hyperfine constants Fermi coupling constants in MHz H 2 O−HO 2 HO 2 T xx T yy −20.4−16.8 T zz −10.9−11.6 Magnetic dipole interaction tensor* in MHz *Principal axis values H 2 O−HO 2 *Ohshima et al. JACS H 2 O–HO 2 –0.040(6)–27.51(2)–27.52(8) H 2 O–OH* 0.940(5)–8.226(6) –74.04 water complexes monomer H 2 OHO 2 /OH HO 2 /OH → Very small induction effect for the electronic structure

Conclusion First observation of the H 2 O–HO 2 radical complex in gas phase. Large binding energy of H 2 O–HO 2, 9.4 kcal/mol, obtained by ab initio calculation is supported by close agreement of the centrifugal distortion constants. Molecular constants provide accurate transition frequencies for remote sensing.