Geometrical phase driven predissociation: Lifetimes of 2^2 A' levels of H_3

TL;DR

This paper investigates how the geometrical phase influences predissociation in H_3, introducing a new computational method to determine vibrational state lifetimes and applying it to H_3's 2^2 A' state.

Contribution

The authors developed a novel method for calculating lifetimes and resonance positions of predissociated vibrational states near conical intersections in triatomic molecules.

Findings

Calculated lifetimes and resonance positions for H_3 vibrational states.

Estimated the three-body recombination rate coefficient for H+H+H.

Demonstrated the significance of the geometrical phase in predissociation dynamics.

Abstract

We discuss the role of the geometrical phase in predissociation dynamics of vibrational states near a conical intersection of two electronic potential surfaces of a D_{3h} molecule. For quantitative description of the predissociation driven by the coupling near a conical intersection, we developed a method for calculating lifetimes and positions of vibrational predissociated states (Feshbach resonances) for X_3 molecule. The method takes into account the two coupled three-body potential energy surfaces, which are degenerate at the intersection. As an example, we apply the method to obtain lifetimes and positions of resonances of predissociated vibrational levels of the 2^2 A' electronic state of the H_3 molecule. The three-body recombination rate coefficient for the H+H+H -> H_2+H process is estimated.