The quantum simulation of large molecular systems is a formidable task. We explore the use of effective potentials based on the Feynman path centroid variable in order to simulate large quantum clusters at a reduced computational cost. This centroid can be viewed as the “most” classical variable of a quantum system. Earlier work has shown that one can use a pairwise centroid pseudo-potential to simulate the quantum dynamics of hydrogen in the bulk phase at 25 K and 14 K [Chem. Phys. Lett. 249, 231, (1996)]. Bulk hydrogen, however, freezes below 14 K, so we focus on hydrogen clusters and nanodroplets in the very low temperature regime in order to study their structural behaviours. The calculation of the effective centroid potential is addressed along with its use in the context of molecular dynamics simulations. The effective pseudo-potential of a cluster is temperature dependent and shares similar behaviour as that in the bulk phase. Centroid structural properties in three dimensional space are presented and compared to the results of reference path-integral Monte Carlo simulations. The centroid pseudo-potential approach yields a great reduction in computation cost. With large cluster sizes, the approximate pseudo-potential results are in agreement with the exact reference calculations. An approach to deconvolute centroid structural properties in order to obtain real space results for hydrogen clusters of a wide range of sizes is also presented. The extension of the approach to the treatment of confined hydrogen is discussed, and concluding remarks are presented.

The quantum simulation of large molecular systems is a formidable task. We explore the use of effective potentials based on the Feynman path centroid variable in order to simulate large quantum clusters at a reduced computational cost. This centroid can be viewed as the “most” classical variable of a quantum system. Earlier work has shown that one can use a pairwise centroid pseudo-potential to simulate the quantum dynamics of hydrogen in the bulk phase at 25 K and 14 K [Chem. Phys. Lett. 249, 231, (1996)]. Bulk hydrogen, however, freezes below 14 K, so we focus on hydrogen clusters and nanodroplets in the very low temperature regime in order to study their structural behaviours. The calculation of the effective centroid potential is addressed along with its use in the context of molecular dynamics simulations. The effective pseudo-potential of a cluster is temperature dependent and shares similar behaviour as that in the bulk phase. Centroid structural properties in three dimensional space are presented and compared to the results of reference path-integral Monte Carlo simulations. The centroid pseudo-potential approach yields a great reduction in computation cost. With large cluster sizes, the approximate pseudo-potential results are in agreement with the exact reference calculations. An approach to deconvolute centroid structural properties in order to obtain real space results for hydrogen clusters of a wide range of sizes is also presented. The extension of the approach to the treatment of confined hydrogen is discussed, and concluding remarks are presented.

No description available.

Acetylacetone (AcAc) exists as a mixture of enol and keto tautomers. Besides providing a good example for the study of tautomerization, it is a model system for investigating intramolecular hydrogen bonds in its enol form. Trapping AcAc in the soft para-Hydrogen (pH2 ) environment brings out new opportunities to investigate its properties. Infrared spectra of the samples give a good characterization of the two stable enol and keto tautomers. The keto/enol ratio in solid pH2 is found to be higher than in other matrices. While vibrational bands of keto are narrow, those of enol are broad, reflecting the intrinsic properties of the enol which exhibits three entangled large amplitude motions (two methyl torsions and the intramolecular hydrogen transfer). Surprisingly, narrowing of some of these bands is observed in a slow time evolution. This effect is interpreted as a consequence of nuclear spin conversion in the hydrogen atoms of the methyl groups, giving access to AcAc species differing by their nuclear spin symmetry. This offers new pertinent investigations on the large amplitude motions, especially on the intramolecular hydrogen transfer. AcAc/pH2 samples have been irradiated by UV laser beams. Irradiation at 266 nm induces isomerization from the stable chelated enol form to non chelated conformers, similarly to the case of other matrices. A clear IR signature of the conformers is obtained thanks to the pH2 host. Irradiation at 248 nm induces the enol/keto tautomerization. The kinetics of this interconversion highlights a non-direct process. Fragmentation is clearly observed under irradiation at 193 nm, followed by chemical reaction with the hydrogen host.

L’acétylacétone (AcAc) existe sous deux formes tautomères, énol et kéto. Sous sa forme énol chélaté, c’est une des molécules les plus simples présentant une liaison hydrogène intramoléculaire. Nous l’avons isolée dans la matrice « quantique » de parahydrogène (pH2) pour étudier ses propriétés en bénéficiant des avantages spécifiques de ce solide cryogénique. Les spectres infrarouges apportent une caractérisation claire des formes énol et kéto. Le rapport kéto/énol est plus important en matrice de pH2 que dans les autres matrices. Les bandes du kéto sont fines alors que certaines bandes de l’énol sont très larges à cause de la présence de la liaison hydrogène. Plusieurs bandes s’affinent très lentement avec le temps. Cet effet surprenant a été interprété en terme de conversion nucléaire de spin dans un groupement méthyle d’AcAc, donnant accès aux spectres de niveaux de torsion différents. Les résultats offrent alors un nouveau moyen d’investigation des mouvements de grande amplitude de la molécule (mouvements couplés de torsion des méthyles et du transfert d’hydrogène interne). La photolyse UV des matrices AcAc/pH2 a été étudiée. Une irradiation à 266 nm conduit à l’isomérisation de l’énol sous différentes formes non chélatées ; des spectres très bien résolus de ces formes sont obtenus grâce aux propriétés du pH2 solide. En irradiant à 248 nm, on observe la tautomérisation vers la forme kéto, l’étude cinétique démontrant que le processus n’est pas direct à partir de l’énol chélaté. Enfin, une irradiation à 193 nm provoque la fragmentation de la molécule, processus qui peut être suivi de réactions avec l’hydrogène de la matrice. / Acetylacetone (AcAc) exists as a mixture of enol and keto tautomers. Besides providing a good example for the study of tautomerization, it is a model system for investigating intramolecular hydrogen bonds in its enol form. Trapping AcAc in the soft para-Hydrogen (pH2 ) environment brings out new opportunities to investigate its properties. Infrared spectra of the samples give a good characterization of the two stable enol and keto tautomers. The keto/enol ratio in solid pH2 is found to be higher than in other matrices. While vibrational bands of keto are narrow, those of enol are broad, reflecting the intrinsic properties of the enol which exhibits three entangled large amplitude motions (two methyl torsions and the intramolecular hydrogen transfer). Surprisingly, narrowing of some of these bands is observed in a slow time evolution. This effect is interpreted as a consequence of nuclear spin conversion in the hydrogen atoms of the methyl groups, giving access to AcAc species differing by their nuclear spin symmetry. This offers new pertinent investigations on the large amplitude motions, especially on the intramolecular hydrogen transfer. AcAc/pH2 samples have been irradiated by UV laser beams. Irradiation at 266 nm induces isomerization from the stable chelated enol form to non chelated conformers, similarly to the case of other matrices. A clear IR signature of the conformers is obtained thanks to the pH2 host. Irradiation at 248 nm induces the enol/keto tautomerization. The kinetics of this interconversion highlights a non-direct process. Fragmentation is clearly observed under irradiation at 193 nm, followed by chemical reaction with the hydrogen host.

No description available.