CH3OH⋯(H2O)n [n = 1-4] clusters in external electric fields.
| Title: | CH3OH⋯(H2O)n [n = 1-4] clusters in external electric fields. |
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| Authors: | Gurav ND; Department of Physics, Savitribai Phule Pune University, Pune 411007, Maharashtra, India.; Kulkarni AD; Centre for Computational Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, Karnataka, India.; Gejji SP; Department of Chemistry, Savitribai Phule Pune University, Pune 411007, Maharashtra, India.; Pathak RK; Department of Physics, Savitribai Phule Pune University, Pune 411007, Maharashtra, India. |
| Source: | The Journal of chemical physics [J Chem Phys] 2015 Jun 07; Vol. 142 (21), pp. 214309. |
| 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: PubMed not MEDLINE |
| Imprint Name(s): | Publication: New York, NY : American Institute of Physics; Original Publication: Lancaster, Pa., American Institute of Physics. |
| Abstract: | For hydrogen-bonded neutral molecular clusters, response to an externally applied electric field can critically affect molecular cooperativity. In this light, response of dilute methanol-water admixtures to an external, perturbative electric field is studied at the simplest molecular level in the cluster configurations CH3OH⋯(H2O)n with "n" chosen to range from 1 to 4, employing the M06-2X hybrid functional in conjunction with the 6-311++G(2d,2p) basis set, well-suited for hydrogen bonding. Methanol is seen to favorably bond with the water molecules at its hydroxyl end up to certain characteristic maximum threshold field strengths beyond which the HOMO-LUMO energy-gap abruptly drops to zero culminating into a complete breakdown of the cluster. In the interim regime prior to breakdown, the electric field significantly alters the hydrogen bonding pattern primarily by elongating the cluster, resulting in a marked enhancement in its electric dipole moment leading to alterations in the molecular electrostatic potential. With the application of electric field, certain "exotic" O-H vibration bands appear that at the threshold field fall in the frequency range of 2510 cm(-1)-1880 cm(-1) in the IR spectra, in contrast with their normal (zero-field) counterparts that occur in the range of ∼3300-3900 cm(-1). |
| Entry Date(s): | Date Created: 20150608 Date Completed: 20150824 Latest Revision: 20150608 |
| Update Code: | 20260130 |
| DOI: | 10.1063/1.4921380 |
| PMID: | 26049498 |
| Database: | MEDLINE |
Journal Article