PhD project overview - REMPI analyses of small, iodine containing molecules

1. PhD project overview -REMPI analyses of small, iodine containing molecules Helgi Rafn Hróðmarsson

2. Presentation overview • Introduction • Courses • Project overview • Publications & conferences • Timeline • Experimental • Theory (diet) • Findings • New states • State Interactions

3. Introduction • Summer internship at Prof. Kvaran‘s research group summers 2009 & 2010. • Study.is – private tutoor since november 2010. • B.Sc. Project under Prof. Kvaran‘s supervision spring 2011. • B.Sc. degree in 2011. • CRI – research & development. • Started as M.Sc. January 2012. • Subsequently switched to PhD. • Plan on finishing late 2015 / early 2016.

4. Courses • Finished courses • Astrophysics 1 (6 ECTS) • Organic Chemistry 3 (6 ECTS) • Inorganic Chemistry 3 (6 ECTS) • Inorganic Chemistry 3 labwork (4 ECTS) • Mathematical analysis IIIB (6 ECTS) • Mathematical analysis IVB (6 ECTS) • Málstofa (1 ECTS) • Total (35 ECTS) • Courses for this semester • Quantum Physics 1 (8 ECTS) • Computational Chemistry (10 ECTS) • Total (18 ECTS) • Grand total (53 ECTS) • Course next semester • Inorganic chemistry 4 (10 ECTS)? • Málstofa (1 ECTS) • Other interesting courses • Modern optics (8 ECTS) • Quantum Physics 2 (8 ECTS) • Astrophysics 2 (8 ECTS) • Electromagnetism (8 ECTS) • Reading course (10 ECTS)

5. Project Overview • REMPI of HI • New states • State interactions • REMPI CH3I • REMPI of I2? • More? • Puplished papers • Jingming Long, HelgiRafnHróðmarsson, Huasheng Wang and ÁgústKvaran, "Photofragmentations, State Interactions and Energetics of Rydberg and Ion-pair states: Two Dimensional Resonance Enhanced Multiphoton Ionization of HBr via singlet-, triplet-, W = 0 and 2 states.  J. Chem. Phys., 136, 214315, (2012) • Helgi Rafn Hróðmarsson, Huasheng Wang and Ágúst Kvaran, New REMPI observations and analysis.for Rydberg and Ion-pair states of HI.  J. Molecular Spectroscopy, 290, p:5-12,  (2013) • In preparation • Helgi Rafn Hróðmarsson, Huasheng Wang and Ágúst Kvaran,  "Photofragmentations, State Interactions and Energetics of Rydberg and Ion-pair states: REMPI of HI" 

6. Future publications • Paper • i) HI – new states #2 • ii) HI – state interactions #2 • iii) Overview paper summerizing the results of REMPI of HCl, HBr, and HI. • iv) Methodology of spectra assignment for HX‘s? • Timeline • Fall 2013 • Fall 2013 • Spring/summer 2014 • Spring/summer 2014

7. Future conferences • EFNÍS conference – October 2013 - Reykjavík • Annual meeting of the Spectroscopy and Dynamics Interest Group of the Royal Society of Chemistry – January 2014 – Oxford

8. Project timeline

9. The project • Two photon excitation to Rydberg and ion-pair states in HI. • Spectra assignments, location of new spectra, previously unobserved, either or both in absorption spectroscopy and REMPI. • Identification and classification of spectral perturbations (via line shifts, intensity alterations and line width deviation) • Excitations in CH3I • Further specifications in analyses pending. • I2? • Other?

10. Experimental setup

11. The project • From a chemist‘s point of view. • Molecular orbitals. • HOMO & LUMO

13. The project • From a physicist‘s point of view. • Hamiltonians • Harmonic oscillator • Rigid Rotor

16. Findings so far (new states) • New states: • Spectra due to two-photon resonance transitions to Rydberg states not previously detected in REMPI but identified in single-photon absorption studies {k3Π0(ν’ = 1) and k3Π1(ν’ = 1)}. • Spectra due to two-photon resonance transitions to Rydberg states, not previously detected {d3Π0(ν’ = 1)}. • Spectra due to two-photon resonance transitions to ion-pair states, not previously detected in REMPI but identified in single-photon absorption studies {V1Σ+(ν’ = m + 8) and V1Σ+(ν’ = m + 9)}. • Spectra due to two-photon resonance transitions to ion-pair states not previously detected {V1Σ+(ν’ = m + 7)}.

18. Other findings in our recent publication • Reassignment of the E and H states. • Assignment of the O1Σ+ state. • Off-resonance interactions leading to the „clenching“ of the V(m+8) ion-pair state.

19. Findings so far (state interactions) – has yet to be published • Both off-resonance and near-resonance interactions between • H1Σ+(1) Rydberg state and the V(m+6) ion-pair state. • O1Σ+(0) Rydberg state and the V(m+7) ion-pair state. • Near-resonance interactions between the I1Δ2(0) Rydberg state and the V(m+9) ion-pair state.

28. Conclusions • Courses will probably be finished at the end of next semester. • If publications go as planned I will have 4-7 published papers early/mid 2014. • Plenty of other research materials on the horizon. • CH3I. I2? • Something overseas? • Already new states have been found in HI as well as numerous, previously unreported, perturbation effects (whose publication is imminent). • Even more new states have already been observed (which are reserved for the latter publication involving new states in HI).

29. Thank you!

30. Supplementary material

33. Intensity ratios, I1Δ2 state

34. Bandwidths, I1Δ2 state