London dispersion dominating diamantane packing in helium nanodroplets

Abstract

Diamantane clusters formed inside superfluid helium nanodroplets were analyzed by time-of-flight mass spectrometry. Distinct cluster sizes were identified as “magic numbers” and the corresponding feasible structures for clusters consisting of...

Diamondoid ether clusters in helium nanodroplets

“…The obtained interaction energies (Table S2, ESI †) for ether clusters CL1-CL3 are in line with our previously obtained values for diamantane clusters 19 and confirm that aggregation of diamondoid ethers in HNDs is indeed an energetically favorable process. As intermolecular LD appears to be the main driving force for the cluster aggregation, increase in cluster size leads to the rise of interaction energies due to multiplication of intermolecular close contacts.…”

“…The choice of the density functional theory (DFT) method was based on our previous benchmarking of similarly bulky molecules in HNDs. 19 We found that the use of Grimme's dispersion correction with Becke-Johnson damping (D3(BJ)), 39,40 the three-body dispersion contributions term implemented in Orca as well as geometrical counterpoise (gCP) correction 43 is desirable in order to account for subtle intermolecular interactions and mitigate the basis-set superposition errors (BSSE), respectively. Zero-point vibrational energy used during the assessment of cluster binding energy was obtained from the semi-empirical quantum mechanical GFN2-xTB method 44,45 at 0.4 K to account for the temperature of the liquid He environment.…”

“…As helium becomes superfluid at low pressures and near-zero Kelvin temperatures, properties like vanishing viscosity and high heat conductivity emerge, 14 making the helium aggregates a suitable medium for trapping weakly binding complexes. 15,16 For example, exceptional properties of HNDs were used to investigate molecular clusters like (V 2 O 5 ) n , 9 weakly bound alkali triplet-dimers 17 and quartet-trimers, 18 diamantane clusters, 19 etc. HNDs are therefore a promising matrix for the generation and analysis of self-organized clusters consisting of diamondoid molecules like adamantane 20,21 and diamantane.…”

“…HNDs are therefore a promising matrix for the generation and analysis of self-organized clusters consisting of diamondoid molecules like adamantane 20,21 and diamantane. 19 Diamondoids belong to a class of naturally occurring, 22 nanometer sized, cage-like hydrocarbons that are mostly superimposable on the cubic diamond lattice. 23,24 As they are hydrogen-terminated, they can be selectively functionalized depending on the envisioned application.…”

“…The experimental findings were supported by a computational analysis, with emphasis on the identified cluster sizes with large abundances, i.e., the magic numbers. Our computational approach was described previously 19 and applied here for the structural analysis of the clusters. To the best of our knowledge, aggregation behavior of diamondoids in HNDs has only been studied for adamantane and diamantane, other diamondoids or their derivatives have remained unexplored up to now.…”