Rovibronic variational calculations of the nitrate radical

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Presentation transcript:

Rovibronic variational calculations of the nitrate radical P. Bryan Changala JILA, National Institute of Standards and Technology and Department of Physics, University of Colorado, Boulder, CO Joshua H. Baraban Department of Chemistry, University of Colorado, Boulder, CO John F. Stanton Department of Chemistry, University of Texas, Austin, TX ISMS 70, UI Urbana-Champaign, IL, 2015

Outline Vibronic coupling of the low-lying electronic states of NO3 Extending the Köppel-Domcke-Cederbaum (KDC) quasi-diabatic vibronic Hamiltonian for rotation Rotational structure of low-lying vibrational levels of the X state Electronic orbital and spin angular momentum effects

The electronic landscape 15000 cm-1 weak coupling strong coupling weak coupling 7000 cm-1 0 cm-1

Adiabatic vs. diabatic Hamiltonians Adiabatic representation: complicated nuclear coord. derivative operators (bad) simple scalar functions of nuclear coordinates (good) KDC quasi-diabatic representation:

KDC-DVR rovibronic Hamiltonian Internal coordinate DVR Rotational function exact curvilinear internal coordinate kinetic energy op. Diabatic KDC-DVR Hamiltonian is extremely sparse Kinetic op. is most expensive, but cost is linear in # of elec. states

Vibronic level structure 5D planar calculation; reproduces results from the EOM-CCSDT vibronic Ham. reported by Simmons, Ichino, and Stanton, J. Phys. Chem. Lett. 3, 1946 (2012). The well-known 1492 cm-1 level; v3 vs. v3+ν4 (v3+v4)^0 (a1’) is very, very low. The variational internal coordinate wavefunctions seem to indicate that it has a lot of ell = 3 character. Presumably mixed with (3v4)^3 (a1’), which is the only a1’ state nearby. (4v4)^0 and (v3+v4)^0 (a2’) are also very mixed and the assignment of the 1522/1569 levels could be just as easily flipped. mixed mixed v3+ν4 manifold, very irregular

Rovibronic level structure Fit low-N 5D variational energies to the same oblate top rotational Heff used for experimental energies [Fujimori et al, J. Mol. Spectrosc. 283, 10 (2013)] Ground vibronic state: Fits from J=0,1 “NO3vibronic_b” dataset 5D rotational energies weren’t done up to 2v4. But with a 4D calculation (no sym. stretch), the zeta constants for v4 and 2v4^2 are very similar (-0.8871 vs. -0.8702), as well as q4 (0.0168 vs 0.0130)

Vibronic contributions to How much vibronic angular momentum comes from z-axis (c-axis) electronic orbital angular momentum in the state? (small!) Indeed, a calculation explicitly including Lz results in no significant change to the rotational structure…

Other roads to L The A state can couple with X vibronically via B, or directly via spin-orbit v. weak quad. coupling strong lin. coupling weak lin. coupling A2’/E’’ is mainly y (also 14 cm^-1 from x) E’/E’ is z X/B SO is vanishing. E’’/E’’ SO is effectively vanishing (though z is allowed); see Lan’s reasoning

Conclusions KDC diabatic Hamiltonian extended to rovibronic treatment of NO3 3-state X/B model does not account for observed Coriolis coupling in vibronically degenerate modes HSO and 5-state X/A/B calculation possibly required Acknowledgements: Lan Cheng (UT Austin) NSF GRFP

DVR vibrational basis “Discrete variable representation” (DVR) basis functions for internal vibrational coordinates highly localized: functions of coordinates, namely Vij(q), are approximately diagonal: