电场
星团(航天器)
分子
化学物理
轨道能级差
化学
领域(数学)
氢键
化学极性
原子物理学
分子物理学
物理
量子力学
计算机科学
有机化学
数学
程序设计语言
纯数学
作者
Nalini D. Gurav,Shridhar P. Gejji,Libero J. Bartolotti,Rajeev K. Pathak
摘要
Response of polar molecules CH3OH and H2O2 and a non-polar molecule, CO2, as “guests” encapsulated in the dodecahedral water cage (H2O)20 “host,” to an external, perturbative electric field is investigated theoretically. We employ the hybrid density-functionals M06-2X and ωB97X-D incorporating the effects of damped dispersion, in conjunction with the maug-cc-pVTZ basis set, amenable for a hydrogen bonding description. While the host cluster (cage) tends to confine the embedded guest molecule through cooperative hydrogen bonding, the applied electric field tends to rupture the cluster-composite by stretching it; these two competitive effects leading to a molecular “tug-of-war.” The composite remains stable up to a maximal sustainable threshold electric field, beyond which, concomitant with the vanishing of the HOMO-LUMO gap, the field wins over and the cluster breaks down. The electric-field effects are gauged in terms of the changes in the molecular geometry of the confined species, interaction energy, molecular electrostatic potential surfaces, and frequency shifts of characteristic normal vibrations in the IR regime. Interestingly, beyond the characteristic threshold electric field, the labile, distorted host cluster fragmentizes, and the guest molecule still tethered to a remnant fragment, an effect attributed to the underlying hydrogen-bonded networks.
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