Model study on the real-time detection of ultrafast nonadiabatic dynamics associated with the Wulf-Chappuis bands of ozone

doi:10.1016/0009-2614(92)87063-U

Chemical Physics Letters

Volume 200, Issues 1–2, 27 November 1992, Pages 163-172

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Abstract

Model calculations on the cw absorption spectrum and femtosecond time-resolved stimulated-emission pump—probe spectra are reported for the Wulf—Chappuis bands of ozone. The model accounts for the three dimensional conical intersection of the ¹A₂ and ¹B₁ excited states and the associated singular non-Born—Oppenheimer coupling. Effects of dissociation into O+O₂ are modelled phenomenologically. It is demonstrated on the basis of this model that detailed information on the ultrafast nonadiabatic excited-state dynamics can be obtained by pump—probe spectroscopy with ultrashort pulses (pulse duration of the order of 10 fs).

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Other examples for the calculation of vibronic coupling parameters can be found in [30,31].
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¹: Postdoctoral fellow of the Deutsche Forschungsgemeinschaft.

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Chemical Physics Letters

Abstract

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On quantifying the vibronic interaction between electronic states

The ozone molecule: Electronic spectroscopy

Diabatic CASSCF orbitals and wavefunctions

Microscopic modelling of photoisomerization and internal-conversion dynamics

Direct construction of diabatic states in the CASSCF approach. Application to the conical intersection of the <sup>1</sup>A<inf>2</inf> and <sup>1</sup>B<inf>1</inf> excited states of ozone

Nonadiabatic coupling and diabatic electronic population dynamics on 1<sup>1</sup>A<inf>2</inf> and 1<sup>1</sup>B<inf>1</inf> states of ozone molecule