Encaged molecules in external electric fields: A molecular "tug-of-war".
| Title: | Encaged molecules in external electric fields: A molecular "tug-of-war". |
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| Authors: | Gurav ND; Department of Physics, Savitribai Phule Pune University, Pune, Maharashtra 411007, India.; Gejji SP; Department of Chemistry, Savitribai Phule Pune University, Pune, Maharashtra 411007, India.; Bartolotti LJ; Department of Physical and Computational Chemistry, East Carolina University, Greenville, North Carolina 27858, USA.; Pathak RK; Department of Physics, Savitribai Phule Pune University, Pune, Maharashtra 411007, India. |
| Source: | The Journal of chemical physics [J Chem Phys] 2016 Aug 21; Vol. 145 (7), pp. 074302. |
| Publication Type: | Journal Article |
| Language: | English |
| Journal Info: | Publisher: American Institute of Physics Country of Publication: United States NLM ID: 0375360 Publication Model: Print Cited Medium: Internet ISSN: 1089-7690 (Electronic) Linking ISSN: 00219606 NLM ISO Abbreviation: J Chem Phys Subsets: MEDLINE; PubMed not MEDLINE |
| Imprint Name(s): | Publication: New York, NY : American Institute of Physics; Original Publication: Lancaster, Pa., American Institute of Physics. |
| Abstract: | 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. |
| Entry Date(s): | Date Created: 20160822 Date Completed: 20170110 Latest Revision: 20170111 |
| Update Code: | 20260130 |
| DOI: | 10.1063/1.4960608 |
| PMID: | 27544100 |
| Database: | MEDLINE |
Journal Article