Asymmetry and coverage dependence in two-pulse correlation measurements of CO photodesorption from Pd(111): Insights from theory

TL;DR

This study combines advanced molecular dynamics simulations with improved energy exchange models to explain asymmetries and coverage effects observed in two-pulse laser experiments on CO desorption from Pd(111).

Contribution

It introduces a refined simulation approach incorporating temperature-dependent electronic properties, successfully reproducing experimental asymmetries and addressing previous underestimations of desorption probabilities.

Findings

Reproduces asymmetry in desorption probability with pulse timing.

Shows importance of temperature-dependent electronic properties.

Reduces discrepancy between theory and experiment at zero delay.

Abstract

Two-pulse correlation experiments performed using pulses of different intensities on Pd(111) with different CO coverages showed that the CO photodesorption probability depends on whether the strong or the weak pulse arrives first to the surface, being this difference particularly large for the low-covered surface. Motivated by these experiments, we perform molecular dynamics simulations using a multicoverage potential energy surface that was previously constructed with the embedded atom neural network method. The process is modeled by combining the two-temperature model (2TM)--to describe the laser-excited electrons and phonons--and Langevin dynamics with electronic time-dependent temperature $T_\textrm{e}$--to model the coupling of the nuclei degrees of freedom with the laser-excited electrons. We show that improving the energy balance description in 2TM--by including \textit{ab-initio} $T_\textrm{e}$-dependent electronic heat capacity and electron-phonon coupling constant--is key to reproduce the asymmetry of the photodesorption probability $P_{\rm des}$ between positive and negative time delays. Furthermore, we also explore possible reasons for the usual underestimation of $P_{\rm des}$ at zero delay given by state-of-the-art calculations. In particular, we improve the description of the energy exchange between CO and the metal surface at high $T_\textrm{e}$ by including in the simulations a $T_\textrm{e}$-dependent friction coefficient. The prediction for $P_{\rm des}$ at zero delay in this case, increases by an order of magnitude, reducing its discrepancy with the experimental value. Altogether, our results hint to the importance of accounting for the temperature dependence of the electronic structure and properties in describing the extreme conditions generated in 2PC experiments.