Argon Solid Response upon Rydberg Photoexcitation of the NO Chromosphore: Case of Using ab Initio Potential Energy Surfaces and Comparison to Similar Studied Systems

Abstract

Molecular dynamics simulations of NO-doped Ar solid upon Rydberg photoexcitation of the impurity have been carried out taking into account angular dependent potential energy surfaces (PESs) in the ground and excited states. To go beyond isotropic potentials simulations, the effects of anisotropy of potentials on the structure, dynamics, and energetics are investigated by taking into account two cases, namely, the whole PESs and the isotropic parts. Results have been compared to those obtained in previous works for similar NO-doped rare gas systems. Radial distribution functions (RDF) for the ground and excited state indicate that for both cases the shell structure of the lattice is kept ordered and is characterized by well-defined bands. No influence of the anisotropy of potentials has been detected in the RDFs since the anisotropy is rather manifested at short distances. The well part, which has been proven to be unimportant for the dynamics in previous works, arises here to be important for the right simulation of the spectrum. In general, our results show a reasonable agreement with respect to the experimental values for the dynamics and energetics when ab initio potentials are used, although better results can be obtained if higher level ab initio PESs are used.

Vibrational relaxation of chloroiodomethane in cold argon

“…39,40 A value of the Debye frequency ω D = 81.374 cm −1 gives a simulation temperature of T = 63 K for the experimental temperature T = 12 K. As will be shown later, the temperature of the bath does not have significant impact on the results.…”

“…It has been reported in the literature that using a higher effective temperature 39,40 in NEMD simulations can incorporate the zero point energy effects. This approach assumes the bath particles behave as simple harmonic oscillators in equilibrium with a heat bath at temperature T. By comparing the quantum and the classical density matrices, a scaled temperature T is obtained…”

Ab Initio Ground- and Excited-State Intermolecular Potential Energy Surfaces for the NO–Ne and NO–Ar van der Waals Complexes

“…Castro-Palacio et al carried out molecular dynamics simulations of NO-doped Ar solid using the potentials available in refs and for the ground and NO(A 2 Σ + )–Ar excited state. The results showed a reasonable agreement with respect to the experimental values for the dynamics and energetics of the complex, and the authors concluded that a better agreement could have been obtained if higher level ab initio IPESs were used.…”