Theoretical investigations for the molecular structures and binding energies for C₆H₆(H₂O) _n , (n = 1–7) complexes

The structure and UV spectroscopy of benzene-water (Bz-W6) clusters using time-dependent density functional theory

“…It is clearly seen from these results that the cage conformer is more stable than the prism conformer, for all of the various functionals employed, as the cage form is found to have higher binding energy (BE) than the prism form, which is also consistent with previous computational studies. 17,40,49 The magnitude of BE's of Bz-W 6 cluster (with ZPE correction) for both the cage and prism forms with different computational methods vary in the following order: LC-wPBE < B2PLYP < wB97X < wB97XD < B2PLYPD < MP2. With ZPE correction, Bz-W 6 cluster is found to be most stable at the MP2 level with the highest BE, and least stable at the LC-wPBE level of calculation.…”

“…Numerous theoretical and experimental studies have been performed on the ground state properties such as binding energies and IR spectra of Bz-W n clusters, and also on noncovalent interactions such as hydrogen bonding interactions that dominate such systems. 1,6,11,[17][18][19][20][37][38][39][40][41] Zwier and their coworkers 15,[18][19][20]22,23,39 have undertaken detailed experimental studies on Bz-W n clusters using resonant ion-dip spectroscopy (RIDIRS) and resonant two-photon ionization (R2PI) techniques. It was observed that the water O-H stretch spectra depends on the size of cluster and is sensitive to the number, strength and the type of hydrogen bonds in which it participates while C-H stretch in benzene was found insensitive to the size of water cluster with n ≤ 7.…”

“…The benzene molecule binds to the water cluster mainly through O-H⋯π hydrogen bonds where one of the free dangling hydrogen atom of the water cluster points toward the π electron cloud of the benzene ring. 17,40,42 Small contributions from C-H⋯O and lone pair (lp)⋯π hydrogen bonded interactions also stabilize the Bz-(H 2 O) 6 cluster. 17 Both cage and prism geometries of water W 6 cluster interact with Bz to give Bz-W 6 cluster and are predicted to retain their cage and prism structures in Bz-W 6 cluster too.…”

Electronic Properties of Hydrogen-Bonded Complexes of Benzene(HCN)1–4: Comparison with Benzene(H2O)1–4

“…The value found for the distance between the water H-atom and the Bz center-of-mass, R H‑cm , 2.411 Å, is, however, slightly larger than that reported by Fredericks et al, 2.302 Å but close to that found by Feller, 2.404 Å at the MP2(FC)/aVDZ theoretical level. On the other hand, both R cm‑cm and R H‑cm are significantly smaller than the recent values reported from DFT B3LYP/aVDZ calculations, 3.594 Å and 2.789 Å, respectively . Although another minimum of the Bz(H 2 O) complex exists, where both H atoms of the water molecule point toward the center of the ring, here, we looked only at that with a single H atom facing the ring, because we are interested in those minima of Bz(H 2 O) n complexes which resemble the most, those of Bz(HCN) n , discussed below.…”

Far-Infrared Investigation of the Benzene–Water Complex: The Identification of Large-Amplitude Motion and Tunneling Pathways

“…Numerous ab initio calculations on the benzene–water complex have been performed. ,, The potential energy surface is very flat, and it is hard to find published values for the structure of minimum electronic energy. Karlstroem et al and Augspurger et al have given global minimum structures, with the water oxygen significantly off the benzene C 6 -axis, indicating a large-amplitude motion of the water molecule in the ground state is needed, to give a cylindrically symmetric average structure.…”