Water-accelerated π-Stacking Reaction in Benzene Cluster Cation

Abstract

Single molecule electron devices (SMEDs) have been widely studied through both experiments and theoretical calculations because they exhibit certain specific properties that general macromolecules do not possess. In actual SMED systems, a residual water molecule strongly affects the electronic properties of the SMED, even if only one water molecule is present. However, information about the effect of H2O molecules on the electronic properties of SMEDs is quite limited. In the present study, the effect of H2O on the ON-OFF switching property of benzene-based molecular devices was investigated by means of a direct ab initio molecular dynamics (AIMD) method. T- and H-shaped benzene dimers and trimers were examined as molecular devices. The present calculations showed that a H2O molecule accelerates the π-stacking formation in benzene molecular electronic systems. The times of stacking formation in a benzene dimer cation (n = 2) were calculated to be 460 fs (H2O) and 947 fs (no-H2O), while those in a trimer cation (n = 3) were 551 fs (H2O) and 1019 fs (no-H2O) as an average of the reaction time. This tendency was not dependent on the levels of theory used. Thus, H2O produced positive effects in benzene-based molecular electronics. The mechanism of π-stacking was discussed based on the theoretical results.

Intermolecular Interaction in Liquid Crystals

“…In this respect, the traditional terminology ''p-p'' stacking is somewhat misleading since it is suggestive of some kind of special interaction between p molecular orbitals. The calculations presented in [33] revealed that a H 2 O molecule accelerates the time of π-stacking formation in a benzene molecular system. The times of stacking formation in the benzene dimer (n = 2) and trimer (n = 3) cations were calculated to be 594 fs (H 2 O) and 922 fs (no-H 2 O), and 566 fs (H 2 O) and 1155 fs (no-H 2 O), respectively.…”

“…Stacking interactions between p systems play a major role in molecular recognition [33][34][35][36][37][38][39], in shaping the structure and the functionality of nucleic acids and in determining the tertiary and quaternary structure of proteins. Vertical stacking between planar molecular systems is favored in polar environment, mainly due to entropic reasons, while electrostatic forces are in general determinant for planar or T-shaped structures in non polar media.…”

“…π-stacking, non-covalent interaction, determining the self-organization of various molecular systems, including discotic LCs [33][34][35][36][37][38][39].…”

Extreme Dynamic Performance of Nanofiber Mats under Supersonic Impacts Mediated by Interfacial Hydrogen Bonds

“…This limitation decreases the ANF−CNT mat's E a * enhancement over CNT mats with increasing strain rate. Moreover, considering the much shorter formation time scales (∼1 ps) 49 of π−π stacking, the strain rate sensitivity on the performance of ANF−CNT mats arises mainly from the time scales associated with the dynamics of hydrogen bonds. Regardless, the 4 and 8 wt % ANF-reinforced CNT mats still outperform the pure CNT mats even at 1 km/s impacts.…”

Parallel-stacked aromatic molecules in hydrogen-bonded inorganic frameworks

“…Moreover, Tachikawa et al have theoretically investigated the ionization dynamics of a benzene cluster. They found that the benzene cluster cation could act as a molecular electronic device by changing the benzene configuration from T-shaped to parallel and that its ON–OFF switching behavior was accelerated by H 2 O molecules 39 .…”