Carbonyl Vibrational Wave Packet Circulation in Mn$_2$(CO)$_{10}$ Driven by Ultrashort Polarized Laser Pulses

TL;DR

This study demonstrates how ultrashort polarized laser pulses can induce and control vibrational wave packet circulation in the degenerate E1 carbonyl stretching modes of Mn₂(CO)₁₀, with potential implications for molecular dynamics manipulation.

Contribution

It provides a detailed quantum dynamical analysis of wave packet circulation in Mn₂(CO)₁₀ driven by ultrashort laser pulses, using advanced computational methods and a DFT-based potential energy surface.

Findings

Wave packet circulation occurs in the E1 modes of Mn₂(CO)₁₀.

Intramolecular anharmonic couplings are negligible over 5 ps.

Excitation conditions strongly influence wave packet compactness.

Abstract

The excitation of the degenerate $E_1$ carbonyl stretching vibrations in dimanganese decacarbonyl is shown to trigger wave packet circulation in the subspace of these two modes. On the time scale of about 5 picoseconds intramolecular anharmonic couplings do not cause appreciable disturbance, even under conditions where the two $E_1$ modes are excited by up to about two vibrational quanta each. The compactness of the circulating wave packet is shown to depend strongly on the excitation conditions such as pulse duration and field strength. Numerical results for the solution of the seven-dimensional vibrational Schr\"odinger equation are obtained for a density functional theory based potential energy surface and using the multi-configuration time-dependent Hartree method.