Unraveling the highly overlapping Ã2B2–B˜2A1 photoelectron bands of Cl2O: Nonadiabatic effects due to conical intersection

Mahapatra, Susanta (2002) Unraveling the highly overlapping Ã2B2–B˜2A1 photoelectron bands of Cl2O: Nonadiabatic effects due to conical intersection The Journal of Chemical Physics, 116 (20). pp. 8817-8826. ISSN 0021-9606

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Official URL: http://aip.scitation.org/doi/abs/10.1063/1.1471905

Related URL: http://dx.doi.org/10.1063/1.1471905

Abstract

The highly overlapping Ã2B2–B˜2A1 photoelectron bands of Cl2O molecule are studied theoretically with the aid of ab initio quantum dynamical methods. The theoretical results are compared with the high-resolution 58.4 nm He I recording of Motte-Tollet et al. [Chem. Phys. 284, 452 (1998)]. The theoretical findings reveal the existence of a conical intersection in the Ã2B2–B˜2A1 electronic manifold of the radical cation (Cl2O+) and the highly overlapping photoelectron bands originate from the associated nonadiabatic interactions. A diabatic vibronic Hamiltonian for the Ã2B2–B˜2A1 interacting manifold of Cl2O+ is constructed in terms of the dimensionless normal coordinates of the neutral Cl2O employing a linear vibronic coupling scheme. The coupling parameters of the Hamiltonian are derived from ab initio electronic structure results. The photoelectron bands are then calculated with this Hamiltonian by solving the eigenvalue equation using a quantum dynamical method and the Lanczos algorithm. The photoelectron bands reveal a prominent progression of the bend vibrational mode and a weak progression of the symmetric stretch vibrational mode of the cation. The vibronic fine structures of the photoelectron bands are carefully examined and an adiabatic ionization energy value of 12.171 eV is estimated for the B˜2A1 band. The impact of nonadiabatic coupling between the Ã2B2 and B˜2A1 electronic states of Cl2O+ on the photoelectron dynamics is also explicitly discussed.

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