Spectroscopy of the NO-Ar Complex in the Vicinity of the 3p ← X 2 Π Transitions in NO Joe Harris SOCAR Group University of Nottingham 68 th International Symposium on Molecular Spectroscopy

StateOrbitalNONO-ArD 0 / cm -1 X2ΠX2Π---88 A2Σ+A2Σ+ 3s C2ΠC2Π3pπ D2Σ+D2Σ+ 3pσ E2Σ+E2Σ+ 4s F2ΔF2Δ3dδ H’ 2 Π3dπ NO Rydberg States of Nitric Oxide StateOrbitalNONO-ArD 0 / cm -1 X2ΠX2Π---88 A2Σ+A2Σ+ 3s C2ΠC2Π3pπ D2Σ+D2Σ+ 3pσ E2Σ+E2Σ+ 4s F2ΔF2Δ3dδ H’ 2 Π3dπ NO C2ΠC2Π3pπ D2Σ+D2Σ+ 3pσ N. Shafizadeh et al., J Chem Phys, 1998, 108, 9313 Y. Kim, H. Meyer, Int Rev Phys Chem, 2001, 20, 219 J. Miller, W. Cheng, J Phys Chem, 1985, 89, 1647 K. Tsuji et al., Chem Phys, 1998, 231, 279

Ground Electronic State Excited Electronic State Ionisation Continuum (2 + 1) REMPI Resonance Enhanced Multiphoton Ionisation Spectroscopy

 Installed a 70mm focal length lens

Tsuji et al New Data K. Tsuji et al., Chem Phys, 1998, 231, 279

Birge-Sponer Analysis  Does not fit to a standard Birge-Sponer plot  Unlikely to be a single state ΔG v+1/2

NO COMPLEX ~ ~ ~ J. Kłos et al., J Chem Phys, 2008, 129,  Better fit with experimental results sought  Calculation of single reference ab initio PESs using RCCSD(T)  Possibility of variational collapse to ground A’ surface

 2 Π degeneracy of C State is lifted through interactions with rare gas atom  Gives rise to two potential energy surfaces of A’ and A” symmetry  Can interact with lower-lying electronic states and potentially collapse to ground state wavefunction ~ ~ ~ ~ ~ ~

Maximum Overlap Method (MOM)  Direct SCF calculation of excited states  Applicable for any SCF method (HF, DFT)  Can be used with post-SCF methods (CC, MPn)  Maintains character of wavefunction  Potential energy surfaces calculated using MOM-HF-MP2/d-aug-cc-pVQZ (BSSE corrected) A. Gilbert et al., J Phys Chem A, 2008, 112, N. Besley et al., J Chem Phys, 2009, 130,

A” A’  Simulations by Jacek Kłos

Experiment Simulation

O. Ershova et al., J Chem Phys, 2013, 138,

V. Tamé-Reyes et al., J Chem Phys, 2012, 137, Conclusions Further Work J. Fleniken et al., J Chem Phys, 1998, 109, 8940

Acknowledgements SOCAR Group: Timothy Wright, Adrian Gardner, Victor Tamé-Reyes, Anna Andrejeva Nicholas Besley, Olga Ershova (Nottingham) Jacek Kłos, Millard Alexander (Maryland) University of Nottingham EPSRC