Signatures of Duschinsky Rotation in Femtosecond Coherence Spectra

Abstract

The motions of nuclei in a molecule can be mathematically described by using normal modes of vibration, which form a complete orthonormal basis. Each normal mode describes oscillatory motion at a frequency determined by the momentum of the nuclei. Near equilibrium, it is common to apply the quantum harmonic-oscillator model, whose eigenfunctions intimately involve combinatorics. Each electronic state has distinct force constants; therefore, each normal-mode basis is distinct. Duschinsky proposed a linearized approximation to the transformation between the normal-mode bases of two electronic states using a rotation matrix. The rotation angles are typically obtained by using quantum-chemical computations or via gas-phase spectroscopy measurements. Quantifying the rotation angles in the condensed phase remains a challenge. Here, we apply a two-dimensional harmonic model that includes a Duschinsky rotation to condensed-phase femtosecond coherence spectra (FCS), which are created in transient–absorption spectroscopy measurements through impulsive excitation of coherent vibrational wavepackets. Using the 2D model, we simulate spectra to identify the signatures of Duschinsky rotation. The results suggest that peak multiplicities and asymmetries may be used to quantify the rotation angle, which is a key advance in condensed-phase molecular spectroscopy.

Keywords

• combinatorics
• harmonic oscillator
• vibronic coupling
• Duschinsky mixing
• femtosecond spectroscopy