The Effects of Electron–Hole Pair Coupling on the Infrared Laser-Controlled Vibrational Excitation of NO on Au(111)

Abstract

In this work, we present theoretical simulations of laser-driven vibrational control of NO adsorbed on a gold surface. Our goal is to tailor laser pulses to selectively excite specific modes and vibrational eigenstates, as well as to favor photodesorption of the adsorbed molecule. To this end, various control schemes and algorithms are applied. For adsorbates at metallic surfaces, the creation of electron-hole pairs in the substrate is known to play a dominant role in the transfer of energy from the system to the surroundings. These nonadiabatic couplings are included perturbatively in our reduced density matrix simulations using a generalization of the state-resolved position-dependent anharmonic rate model we recently introduced. An extension of the reduced density matrix is also proposed to provide a sound model for photodesorption in dissipative systems.

Effect of surface temperature on quantum dynamics of D2 on Cu(111) using a chemically accurate potential energy surface

“…TDDVR 6D QD outcomes 42 In the realm of surface science, elhp excitations impart substantial effects on the dissociative chemisorption, inelastic scattering, and external field induced (vibrational excitation, relaxation, dissipation, and non-adiabatic electron transfer) phenomena. 46,[108][109][110][111][112][113][114][115] In this context, various theoretical approaches, namely, electronic friction (EF) 88 [local density friction approximation (LDFA) 46 and orbital dependent friction (ODF) 46,116,117 ], independent electron surface hopping (IESH), 112,118 reduced density matrix, [119][120][121] EH (phonon + elhp), 105,106 and stochastic wave packet approach, 122 have been developed during the past few decades. Those theoretical treatments unveiled the crucial contribution of elhp excitations on the state-to-state vibrational transition probabilities at higher surface temperature situations.…”

A unifying model for non-adiabatic coupling at metallic surfaces beyond the local harmonic approximation: From vibrational relaxation to scanning tunneling microscopy

“…These constraints are not met for most molecule-surface systems, where multiple minima are connected by low-energy barriers along large amplitude diffusion coordinates. Only recently were these limitations addressed adequately, [38][39][40] where the adsorbate was embedded in an electron gas of variable density to mimic the position-dependence of the non-adiabatic coupling. In the model, numerical integration of the gradient operator was used to ensure proper treatment of anharmonicity.…”

“…It is the main goal of the present work to develop a physically sound model that goes beyond these limitations while keeping its most attractive features. Since the position-dependent anharmonic rate model introduced recently [38][39][40] cannot be extended straightforwardly to treat STM-induced excitations, an alternative derivation is proposed. To avoid the pitfalls associated with the identification and the characterization of a single adsorbate resonance, the model of Gao et al [49][50][51][52] is reinterpreted using source-bridgesink terminology, where the source and sink density of states are projected on a physical bridge state located at the position of the adsorbate, hence allowing to recover the positiondependence of the non-adiabatic couplings.…”