1. Electron Collision Data of C-H &C-F Compound Molecules for Plasma Modeling Present Status of Our Research Proposal Hiroshi Tanaka Department of Physics Sophia University, Tokyo, JAPAN 2 nd Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Program on” Atomic and Molecular Data for Plasma Modeling” IAEA, Vienna, Austria 19 Jun. 2007

2. TITLE OF RESEARCH TOPIC proposed 2005-2006 Electron Collision Data of C-H Compound Molecules for Plasma Modeling 2007 Electron Collision Data of C-H & C-F Compound Molecules for Plasma Modeling

3. PROJECT PERSONNEL Chief Scientific Investigator: Hiroshi TANAKA (Prof. Sophia Univ. JAPAN) Other Supporting Scientific Staff: Masamitsu HOSHINO (Dr. Sophia Univ. JAPAN) Mineo KIMURA (Prof. Kyushu Univ. JAPAN) Michael J. BRUNGER (Prof. Flinders Univ. AUSTRALIA) Stephen J. BUCKMAN (Prof., Australian Nat’l Univ. AUSTRALIA) Casten MAKOCHEKANWA (Dr. Australian Nat’l Univ. AUSTRALIA ) Hyuck CHO (Prof. Chungnam Nat’l Univ. South KOREA)

4. A: Results for the project Summary of WORK PLAN proposed (in 2005) Year 1: Evaluation and analysis of related data available in literature but scattered in different places all over the world within the framework of IAEA International Bulletin on Atomic and Molecular Data for Fusion. Year 2: Compilation and addition of new data from our group as well as from other research groups to the database. In the same process, data from our group will be systematically compiled for the more than 30 molecules studied so far for the collision processes: elastic, vibrational and electronic excitations, and total cross sections. Year 3: Proposal of new directions for producing missing but necessary experimental and theoretical data for these processes related to fusion and plasma processing plasmas.

5. Outlook (presented in 2005) EELS: Elastic Scattering: C 3 H 6 C 3 F 6 COF 2 Vibrational Excitation : C 3 H 6 C 3 F 6 COF 2 Electronic Excitation : C 3 F 6 COF 2 (H 2 O, DNA bases) QMSS: Radical Detection: CH x (X = 3  0) from CH 4 Our Data Base to be prepared in IAEA,NIFS Report, and AAMOP

6. Results (publication list related to IAEA) 1) Experimental and theoretical elastic cross sections for electron collisions with the C 3 H 6 isomers, C. Makochekanwa et al, J. Chem. Phys. 124 024323-1 (2006) 2) Experimental observation of neutral radical formation from CH 4 by electron impact in the threshold region, C. Makochekanwa et al, Phys. Rev. A 74 042705 (2006) 3) Low energy electron energy-loss spectroscopy of CF 3 X (X=Cl, Br), M. Hoshino et al, J. Chem. Phys. 126 024303 (2007) 4) Electron and positron scattering from 1,1-C 2 F 2 H 2, C. Makochekanwa et al, J. Chem. Phys. 126 164309-1 (2007)

7. Activities on Data Compilation Our Data Base has been prepared as IAEA & NIFS Report, and a revised version will be arranged for IAEA Bulletin, Ad. At. Mol. Opt. Phys, or J. Chem. Phys. Data The Projects for NIFS (2003-2006) and JAERA(2004-2006), in Japan, were accomplished in the last fiscal year, this March

8. Role of NIFS NETWORK ＮＩＦＳ, KAERI, & NFRC ＮＥＴＷＯＲＫ Research Institute Industry University Research Society Individual

9. IAEA & NIFS report (to be submitted): Elastic Differential Cross Sections for Electron Collisions with Polyatomic Molecules IAEA bulletin (being prepared): Database for Electron Collisions with Polyatomic Molecules: Elastic- and Resonant Vibrational Excitation-Differential Cross Sections Report for Database for electron collision with polyatomic molecules

10. IAEA & NIFS Report (2007) Elastic Differential Cross Sections for Electron Collisions with Polyatomic Molecules M. Hoshino 1, H. Kato 1, C. Makochekanwa 1, 2, S.J. Buckman 2, M. J. Brunger 3, H. Cho 4, M. Kimura 5, D. Kato 6, I. Murakami 6, T. Kato 6, and H. Tanaka 1 1 Department of Physics, Sophia University, Tokyo 102-8554, Japan 2 Center for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Australia 3 Center for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia 4 Department of Physics, Chungnam National University, Daejeon 305-764, Korea 5 Graduate School of Sciences, Kyushu University, Fukuoka 812-8581, Japan 6 National Institute of Fusion Science, Toki 509-5292, Japan 1 Introduction 2 Definition of Cross Sections 3 Experimental Techniques for Precision Measurement of Elastic DCS 4 Benchmark Cross Section for Elastic DCS A. Fusion Plasma-Related Gases B. Processing Plasma-Related Gases C. Environmental Issues-Related Gases 5 Concluding Remarks This work is supported partially by the IAEA, CUP, MEXT, and ARC

11. List of Molecules tabulated in this report A. Fusion Plasma-Related Gases CH 4, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, isomers- C 3 H 4 B. Processing Plasma-Related Gases CF 4, C 2 F 6, C 3 F 8, C 3 F 6, cyclo -C 4 F 8, C 2 F 4, C 6 F 6, CH 3 F, CH 2 F 2, CHF 3, CF 3 I NF 3, SF 6 SiH 4, Si 2 H 6, GeH 4 C. Environmental Issues -Related Gases CF 3 Cl, CF 3 Br H 2 O, CO 2, N 2 O

12. New Version for IAEA Bulletin, Ad. At. Mol. Opt. Phys., or J. Chem. Phys. Data Database for Electron Collisions with Polyatomic Molecules: Elastic- and Resonant Vibrational Excitation -Differential Cross Sections M. Hoshino 1, H. Kato 1, C. Makochekanwa 1, 2, S.J. Buckman 2, M. J. Brunger 3, H. Cho 4, M. Kimura 5 and H. Tanaka 1 1 Department of Physics, Sophia University, Tokyo 102-8554, Japan 2 Center for Antimatter-Matter Studies, Australian National University, Canberra ACT 0200, Australia 3 Center for Antimatter-Matter Studies, Flinders University, Adelaide SA 5001, Australia 4 Department of Physics, Chungnam National University, Daejeon 305-764, Korea 5 Graduate School of Sciences, Kyushu University, Fukuoka 812-8581, Japan 1 Introduction 2 Definition of Cross Sections 3 Experimental Techniques for Precision Measurement of Elastic DCS 4 Benchmark Cross Section for Elastic DCS A. Fusion Plasma-Related Gases B. Processing Plasma-Related Gases C. Environmental Issues-Related Gases 5 Resonant Vibrational Excitations 6 Concluding Remarks This work is supported partially by the IAEA, CUP, MEXT, and ARC

13. SUMMARY of ACTIVITIES for DATABASE from 2005 to 2008 Target Molecules: H-C Molecules produced from the internal wall materials of fusion chambers H-C & C-F Molecules for plasma processing Research directions for the first two years: 2005: compilation and analysis of data already available in literature that relates to this filed of plasma modeling 2006: analyzing recent data from our collaboration group in conjunction with related data from other laboratories on cross sections from these molecules Our Database compiled is restricted only to our own elastic DCS

14. Research directions for 2008 and in future: 2008: propose directions for experimentalists and theorists to come up with new cross section data that would make the database for each molecule as complete as feasible as relates to the application to the fusion- and plasma processing- plasmas (proposed 2005) Furthermore, being proposed as follows: Experimental Verification for BEf - Scaling Law in Electron-Molecule Collision continued

15. Data Needs for Data Needs for Electron collision cross section of plasma-relevant gases – present and future H.TANAKA and M. HOSHINO Department of Physics Sophia University Tokyo, Japan 2 nd Research Co-ordination Meeting of the IAEA’s Co-ordinated Research Program on ” Atomic and Molecular Data for Plasma Modeling” IAEA, Vienna, Austria 19 Jun. 2007 B: Progress in the project

16. Collaboration International Chugnam National University ( Prof. Cho S. Korea) Australian National University (Prof. Buckman AU) Flinders University of Southern Australia (Prof. Brunger AU) The Open University (Prof. Mason UK) NIFS (Dr. Y.-ki Kim deceased) Domestic Kyushu University (Prof. Kimura, Collaboration Theoretical) NIFS (Prof. Kato under the Japan-Korea CUP program) JAERI (Dr. Kubo under the Fusion Plasma Project in Japan) Tohoku University(Prof. Ueda, SR experiment at Spring-8) RIKEN (Prof. Yamazaki, Highly Charged Ion Research)

17. Group Members Dr. M. Hoshino (Assist. Prof.) : T. Tanaka (D3) : SR Experiment H. Kato (D2) : EELS H. Kawahara (M1) : EELS Y. Nagai (M1) : EELS Kobayashi (M1) : Threshold Electron Spectroscopy by TOF Tomita (M1) : Positron Experiment Ishii (M1) : Negative Ion & LEED ( now in US) Kanazawa( M1) : Capillary Experiment on Highly Charged Ion

18. Data providers (Atomic physicists) * theory * experiment Data users in various application fields * fusion science * astrophysics * industrial plasmas * environmental physics * medical (radiotherapy) etc. Data centers data compilation data evaluation (important but not easy) dissemination and updating of database retrievable online database = easy to access, use, find data Data requests Data needs Data provide Data search Hard to find or request data Data search for check International A&M data center network IAEA, NIFS, NIST, ORNL, GAPHIOR, etc. Data provide feedback Views from Database assessed data on electron collision cross sections

19. Research Sites SPring-8 RIKEN Sophia electronpositron photon ion scattered electron ejected electron secondary-photo -Auger-electron positive / negative ion, radical Atom Atom Molecule Molecule Surface Surface Science Univ. of Tokyo Photon Factory

20. Electron Interactions with Molecule Collision Processes of Interest Quantitative Differential Cross Section Measurements Electron Energy-loss Spectroscopy (EELS): Elastic Scattering DCS Resonant Phenomena in Vibrational Excitation Electronic Excitation Process, GOS Quadra- Pole- Mass Spectroscopy (QMSS) Non-radiative Dissociation Products (Threshold Ionization Spectroscopy) Dissociative Attachment Processes Low Energy Electron Diffraction (LEED) Surface and Phase Transition (previously presented in 2005)

21. Definition of various Cross Section ・ Differential Cross Section for channel “n” ・ Integral and Momentum transfer Cross Section Crossed beam method ・ Total Cross Section Transmission experiment Swarm experiment ※ Upper limit of cross sections Boltzmann equation Measurements of electron collision-cross sections

22. On-going and Near -future Measurements EELS: Elastic Scattering: (CH 3 )O, C 6 H 5 X (X=H, CH 3, CF 3 ) Vibrational Excitation : (CH 3 )O, C 6 H 5 X (X=H, CH 3, CF 3 ), CH 3 X (X=I, Br), (CH 3 )O Electronic Excitation : H 2, CO, NO, H 2 O, C 6 H 5 X (X=H, CH 3, CF 3 ) CH 3 X(X=I, Br) Excited Molecular Target: vibratinally excited H 2, CO 2 (in progress) QMSS: Radical Detection: CH x (X=1,2,3) from CH 4 Negative Ion Detection: CH 4, F 2 CO & Condensed-Phase (in progress) LEED: Anti-ferromagnetic Surface: NiO, CoO, FeO (in progress) SR: Inner-shell soft X-ray photoelectron & Auger electron spectroscopy

23. Collision Data for Molecules by Electron Impact investigated at Sophia University CH 4, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 4, C 3 H 6 CF 4, C 2 F 6, C 3 F 8, C 2 F 4, c-C 4 F 8, C 6 F 6, C 3 F 6 CF 3 H, CF 2 H 2, CFH 3, CH 3 I, CH 3 Br CF 3 Cl, CF 3 Br, CF 3 I CF 2 Cl 2, CFCl 3, 1,1-C 2 F 2 H 2 SiH 4, Si 2 H 6, SiF 4, GeH 4 NF 3, C 60, C 6 H 6, C 6 H 5 CH 3, C 6 H 5 CH 3, (CH 3 ) 2 CO N 2 O, CO 2, COS, H 2 O, CS 2, XeF 2, HCN H 2 CO H 2, CO, N 2, NO, He (molecules marked pink after the 1 st RCM)

24. 1)EELS Why (CH 3 ) 2 O and C 6 H 5 X (X=H, CH 3, CF 3 )? (CH 3 ) 2 O: Alternative of the car fuel C 6 H 5 CH 3 and C 6 H 6 : Volatile Organic Molecule (VOC), Chemical Hazard regulated under the PRTR (Pollutant Release and Transfer Register )

25. VOC (volatile organic molecule) Toluene: VOC (volatile organic molecule) C 6 H 5 CH 3, C 6 H 5 CF 3 C6H6C6H6 PRTR (Pollutant Release and Transfer Register) PRTR (Pollutant Release and Transfer Register) Atmospheric Discharge Plasma

26. Elastic DCS Comparisons of C 6 H 6, C 6 H 5 CH 3 and C 6 H 5 CF 3 H. Cho et al., J. Phys. B 34, 1019 (2001).

27. Energy Loss Spectrum of Toluene - vibrational excitation Loss 0.17eV CH 3 umbrella mode CH 3 asym bending aromatic C=C Loss 0.38eV aromatic C-H streching CH 3 asym streching sym streching

28. Total Cross Section & Resonant Vibrational Excitation

29. Vibrational Excitation Functions for the stretching vib. modes

30. e- shape resonance e- direct scattering e-e- e-e- Shape resonance

31. Substituting effects on Electronic Excitation

32. Y.-K. Kim and M. E. Rudd, Phys. Rev. A 50, 3954 (1994) BE f -scaling proposed by Yong-ki Kim Deduction of unavailable data 1. Ionization cross section

33. 2. Optically allowed electronic excitation for Atom

34. BE f -scaling proposed by Yong-ki Kim 3. Electronic excitation cross sections in CO

35. DCS for v =2 of the A state in CO

36. GOS of v =2 of the A state in CO

37. Concepts of Yong –ki Kim’s Theory We use the BEf - scaling on  Born where T = incident energy of the electrons B = Binding energy E = Excitation Energy f accu = accurate optical oscillator strength (OOS) value f Born = value of the optical oscillator strength obtained from the same wavefunctions used to calculate  Born

38. Generalised oscillator strengths (GOS) for the A 1  (=7)  X 1  +(  =0) excitation of CO are available from Chantranupong et al The GOS must be integrated over angles ( ≡ momentum transfer K a0 ) to get  Born. This is achieved using the analytic formula of Vriens with one fitting constant a: Here we also use the accurate OOS for the A 1  state from Berkowitz Scaling parameters for CO

40. Comparisons for the ICS the scaling & the present data

41. ITER (International Thermonuclear Reactor) Data Needs for Carbon impurities (H/D-C molecules) produced by physical and chemical sputtering CH/D 3, CH/D 4, C 2 H/D 2, C 2 H/D 4, C 2 H/D 6, C 3 H/D 8 Vibrationally (Hot) excited Molecules H 2, D 2

42. Neutral Radical Detection- ionization threshold spectroscopy Parent neutral CH 4 + CH 3 + CH 2 + CH + C+C+ CH 4 12.614.315.122.225 CH 3 9.815.117.725 CH 2 10.317.420.2 CH13.020.3 C16.8 Table 1. Ionization thresholds e + CH 4 CH 3 + H + e e + CH 3 CH 3 + +2e

43. Non-radiative CH 3 Radical from CH 4 by Electron Impact

44. Radical production near threshold ？

45. Electronic excitation of CH 4 by electron impact ― Optical excitation spectrum H.H.Brongersma and L. J. Oosterhoff, Chem. Phys.Lett. 3 437 (1969) 1 3 T 2 1 1 T 2 E thr 1 1 T 2 : 8.5 eV 1 3 T 2 : 7.5 eV Threshold Energy

46. Comparison of present and optical results K. Kameta, N. Kouchi, M. Ukai, Y. Hatano J. Electron Spectrosc. Relat. Phenom. 123, 225 (2002)

47. 1 3 T 2 Low Lying 3 T 2 contribution for producing CH 3 8.5 eV 1 1 T 2 + Other channels

48. Higher electronic excitation states Jahn-Telle r 4s Rydberg

49. Negative ion formation on CH 4 + e CH 4 + e  CH 3 - CH 2 - CH - C - ? gas phase or surface ?

50. Electron impact cross section from vibrationally excited CO2

51. 0deg ARIY spectra 100 180 100 Bond angle (deg) Energy (arb. units) Electronic ground state 2 =0 2 =1 Photon Energy B 1 state (linear) A 1 state (bent) 1s  *core excited states h Synchrotron Radiation Experiments : hot Molecules CO 2 : Molecular Properties

52. Angle resolved ion yield spectra of hot-CO 2  resonance T. Tanaka et al, PRL 95 203002 (2005)

53. Angle resolved ion yield spectra of hot-N 2 O in the region of shape resonance in the region of shape resonance T. Tanaka et a, PRL submitted

54. Outlook EELS: Elastic Scattering: CH 3 )O, C 6 H 5 X (X=H, CH 3, CF 3 ) Vibrational Excitation :CH 3 )O, C 6 H 5 X (X=H, CH 3, CF 3 ), CH 3 X (X=I, Br), (CH 3 )O Electronic Excitation : H 2, CO, NO, H 2 O, C 6 H 5 X (X=H, CH 3, CF 3 ), CH 3 X(X=I, Br) QMSS: Radical Detection: CH x (X=1,2,3) from CH 4 Negative Ion Detection: CH 4, F 2 CO & Condensed-Phase (in progress) QMSS: Radical Detection: CH x (X=1,2,3) from CH 4 Negative Ion Detection: CH 4, F 2 CO & Condensed-Phase (in progress) Database prepared for IAEA &NIFS Report SR: Inner-shell soft X-ray photoelectron & Auger electron spectroscopy Excited Molecular Target: vibratinally excited H 2, CO 2 (in progress) A revised Database being prepared for AAMOP

55. Molecules investigated A. Fusion Plasma-Related Gases CH 4, C 2 H 6, C 3 H 8, C 2 H 4, C 3 H 6, isomer- C 3 H 4 B. Processing Plasma-Related Gases CF 4, C 2 F 6, C 3 F 8, C 3 F 6 cyclo -C 4 F 8, C 2 F 4, C 6 F 6, CH 3 F, CH 2 F 2, CHF 3 NF 3, (SF 6 ) SiH 4, Si 2 H 6, GeH 4, SiF 4 F 2 CO C. Environmental Issues -Related Gases CF 3 Cl, CF 3 Br, CF 3 I, CF 2 Cl 2, CFCl 3 CO 2, N 2 O,( H 2 O), OCS, CS 2 H 2 CO, C 6 H 5 X(X=H,CH 3,CF 3 ), (CH 3 ) 2 O, CH 3 I

56. Review Articles previously published Review articles after 1990, 1. International Bulletin on Atomic and Molecular Data for Fusion, 42(1992)-58(2000) published by IAEA, 2. Collision Data Involving Hydro-Carbon Molecules, H. Tawara, Y. Itikawa, H. Nishimura, H. Tanaka, and Y. Nakamura, NIFS-DATA-6 July (1990) 3. Atomic Data and Nuclear Data Tables 76 (2000) 1 4. One Century of Experiments on Electron-Atom and Molecule Scattering: a Critical Review of Integral Cross-sections Ⅱ -Polyatomic Moecules, Ⅲ -Hydrocarbons and Halides, G. P. Karwasz, R. S. Brusa, and A. Zecca, La Rivista del Nuvo Cimento 24 (1) (4) 2001 5. Analytic Cross Sections for Electron Collisions with Hydrocarbons: CH 4, C 2 H 6, C 2 H 4, C 2 H 2, C 3 H 8, and C 3 H 6, T. Shirai, T. Tabata, H. Tawara, and Y. Itikawa, Atomic Data and Nuclear Data Tables 80, 147-204 (2002) 6. Interaction of Photons and Electrons with Molecules, M.J.Brunger and S.J.Buckman, Photon and Electron Interactions with Atoms, Molecules, and Ions, vilI/17, sub-volume C ed Y. Itikawa, Landorf-Beurnstein (2003, Berlin: Springer) p6-118 7. Collision Processes of C 2, 3 H y and C 2, 3 H y Hydrocarbons with electrons and Protons R. K.Janev and D. Reiter, Phys. Plasma 11 (2004) 780 8. Vibrational Excitation of Polyatomic Molecules by Electron Collisions Y. Itikawa, J. Phys. B: At. Mol. Opt. Phys 37 R1-24 (2004)