Vibrational energy relaxation of interfacial OH on a water-covered α-Al₂O₃(0001) surface: a non-equilibrium ab initio molecular dynamics study

Abstract

Vibrational dynamics and relaxation of excited non-hydrogen bonded OH-aluminols from non-equilibrium AIMD, towards in silico time-resolved VSF experiments.

Vibrational spectroscopy by means of first‐principles molecular dynamics simulations

“…Reprinted with permission from Ref. [226]; permission conveyed through Copyright Clearance Center, Inc…”

Computational vibrational spectroscopy of molecule–surface interactions: what is still difficult and what can be done about it

“…48 It has been applied in a limited way to compute spectra at solid interfaces, for example (liquid) water on CaF 2 , 49 hydroxylated and (deuterated) water-covered alumina surface. 50,51 It has not established itself in mechanistic studies of molecule-surface systems, in particular in the field of heterogeneous catalysis. A major difficulty is the absence of potential energy surfaces for most (an overwhelming majority) molecule-surface systems studied in laboratories.…”

Vibrational Dynamics at Aqueous–Mineral Interfaces

“…Recently, Saalfrank and co-workers implemented nonequilibrium AIMD (NE-NVE/AIMD) simulations to excite upright non-hydrogen-bonded aluminol groups at the water covered α-Al 2 O 3 (0001)/H 2 O interface (Figure 19). 101 The authors chose to focus on the excitation of weakly hydrogen-bonded aluminol groups, which were orientationally flexible and at room temperature were able to switch between upright and parallel with the surface. It was found that, following excitation of the upright aluminol groups, energy transfer directly to the alumina surface phonons was not significant in the relaxation process.…”

“…Although the system was constrained in size and scope by the cost of the simulations, Saalfrank and coworkers mentioned that the NE-NVE/AIMD approach is not limited in the ways that a parametrized force field is, allowing for the method to be implemented in other avenues. 101…”

“…The authors concluded that generally the hydrogen-bonding modes located between 3000 and 3500 cm –1 act as efficient pathways for vibrational relaxation and redistribution of injected kinetic energy into the system from excited non-hydrogen-bonded aluminol groups. Although the system was constrained in size and scope by the cost of the simulations, Saalfrank and co-workers mentioned that the NE-NVE/AIMD approach is not limited in the ways that a parametrized force field is, allowing for the method to be implemented in other avenues Figure summarizes the findings of the transient work performed at the Al 2 O 3 /H 2 O interface reviewed here.…”