A simple but accurate potential for the naphthalene-argon complex: Applications to collisional energy transfer and matrix isolated IR spectroscopy

Abstract

An explicit polarizable potential for the naphthalene-argon complex has been derived assuming only atomic contributions, aiming at large scale simulations of naphthalene under argon environment. The potential was parametrized from dedicated quantum chemical calculations at the CCSD(T) level, and satisfactorily reproduces available structural and energetic properties. Combining this potential with a tight-binding model for naphthalene, collisional energy transfer is studied by means of dedicated molecular dynamics simulations, nuclear quantum effects being accounted for in the path-integral framework. Except at low target temperature, nuclear quantum effects do not alter the average energies transferred by the collision or the collision duration. However, the distribution of energy transferred is much broader in the quantum case due to the significant zero-point energy and the higher density of states. Using an ab initio potential for the Ar-Ar interaction, the IR absorption spectrum of naphthalene solvated by argon clusters or an entire Ar matrix is computed via classical and centroid molecular dynamics. The classical spectra exhibit variations with growing argon environment that are absent from quantum spectra. This is interpreted by the greater fluxional character experienced by the argon atoms due to vibrational delocalization.

Rates of Molecular Vibrational Energy Transfer in Organic Solutions

“…Coupling to solvent may however transfer energy to translational motion of the solvent molecules. Our study is based on classical simulations, in line with extensive previous work both for gas-phase 24,25 and condensed phase [11][12][13][14]18 examples.…”

Interactions of benzene, naphthalene, and azulene with alkali-metal and alkaline-earth-metal atoms for ultracold studies

“…Cold collisions and sympathetic cooling of molecules as large as benzene were theoretically investigated only for mixtures with helium and other rare-gas atoms [40][41][42][43][44][45] . Intermolecular interactions of benzene and naphthalene with raregas atoms were investigated theoretically and experimentally [46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] . Unfortunately, there is very limited knowledge of cold interactions and collisions between large polyatomic molecules and alkali-metal or alkaline-earth-metal atoms, hence prospects for sympathetic cooling of such molecules down to low and ultralow temperatures are not known.…”

Small and Efficient Basis Sets for the Evaluation of Accurate Interaction Energies: Aromatic Molecule–Argon Ground-State Intermolecular Potentials and Rovibrational States

“…The intermolecular vibrations were evaluated, and some experimentally observed bands reassigned. In 2013, a simple IPES based on electronic structure data but with different form allowing some natural extension to model multiple argon atoms and the intramolecular dynamics of naphthalene was obtained . This potential was derived from CCSD(T)/aug-cc-pVDZ ab initio interaction energies.…”