Metastable States Arising from the Ablation of Solid Copper 69th International Symposium on Molecular Spectroscopy Metastable States Arising from the Ablation of Solid Copper Anna Andrejeva, Joe P. Harris, Timothy G. Wright School of Chemistry, University of Nottingham, UK

Introduction Copper is found in many proteins - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Copper is found in many proteins Interactions in such systems are still poorly understood Use small molecules (eg. CuSH, CuSMe) as simple models for copper binding in biological systems

Experimental Setup Motor Assembly Copper Rod General Pulsed Valve Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Motor Assembly Copper Rod General Pulsed Valve PEEK Nozzle

Atomic Copper Spectra 3 d 10 4p ← 3 d 10 4s 3 d 10 𝑛d ← 3 d 10 4s Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions 3 d 10 4p ← 3 d 10 4s 3 d 10 𝑛d ← 3 d 10 4s

Atomic Copper Spectra Phys. Lett. A, 372, 4805 (2008) Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Phys. Lett. A, 372, 4805 (2008) Phys. Rev. A, 59, 873 (1999)

Analysis of nd Rydberg Series Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Observed position / cm-1 Assignment 60 056.6 3d108d 60 596.0 3d109d 60 597.2 3d1010d 61 214.8 3d1011d 61 407.2 3d1012d 61 554.0 3d1013d 61 661.6 3d1014d 61 754.4 3d1015d 61 825.2 3d1016d 61 883.2 3d1017d 1] J. Opt. Soc. Am., 63, 346 (1973) 2] Phys. Rev. A, 59, 873 (1999) 3] Phys. Lett. A, 372, 4805 (2008) Current Study Tondello1 Simard2 Bellert3 Ionisation Energy / cm-1 62 316 62 317 62 318 Quantum Defect 1.015 - 1.018 0.92 I.E. = 62 316 cm-1 δ = 1.015 𝐸 𝑟 =𝐼.𝐸. − 𝑅 (𝑛 − 𝛿) 2

Extra peaks in one-colour spectrum? Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Wavenumber / cm-1

3 d 10 4s 3 d 9 4 s 2 → 2𝐷 → 2 𝐷 3 2 3 d 9 4s4p Metastable States Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions 3 d 9 4 s 2 → 2𝐷 → 2 𝐷 3 2 2 𝐷 5 2 3 d 10 4s 3 d 9 4s4p 2𝐷 5 2 4𝑃 1 2 4𝐹 5 2 4𝐹 3 2 4𝐷 7 2 4𝐹 9 2 4𝑃 3 2 4𝐷 5 2

Transitions from Metastables Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions 2 D 5 2 (3 𝑑 9 4 𝑠 2 ) 𝟐𝑺 (𝟑 𝒅 𝟏𝟎 𝟒𝒔) 4 F 9 2 (3 𝑑 9 4𝑠4𝑝) * * * * * (+K!) * * * * * * * Wavenumber / cm-1

Metastable Production Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions Ablation laser power Backing pressure Excitation laser power Timings Extraction voltages Wavenumber / cm-1

Conclusions Recorded (1+1′) and (2+1) REMPI spectra Observed 2 P 1 2 , 3 2 states Observed nd Rydberg series Observed additional bands arising due to transitions from metastable initial states Introduction - Motivation Experimental - Ablation source Results - Copper spectra - Rydberg Analysis - Metastable States Conclusions

Acknowledgments Prof. Timothy G. Wright Anna Andrejeva