The influence of large-amplitude librational motion on the hydrogen bond energy for alcohol-water complexes
(2015) In Physical Chemistry Chemical Physics 17(37). p.23761-23769- Abstract
- The far-infrared absorption spectra have been recorded for hydrogen-bonded complexes of water with methanol and t-butanol embedded in cryogenic neon matrices at 2.8 K. The partial isotopic substitution of individual subunits enabled by a dual inlet deposition procedure provides for the first time unambiguous assignments of the intermolecular high-frequency out-of-plane and low-frequency in-plane donor OH librational modes for mixed alcohol-water complexes. The vibrational assignments confirm directly that water acts as the hydrogen bond donor in the most stable mixed complexes and the tertiary alcohol is a superior hydrogen bond acceptor. The class of large-amplitude donor OH librational motion is shown to account for up to 5.1 kJ mol(-1)... (More)
- The far-infrared absorption spectra have been recorded for hydrogen-bonded complexes of water with methanol and t-butanol embedded in cryogenic neon matrices at 2.8 K. The partial isotopic substitution of individual subunits enabled by a dual inlet deposition procedure provides for the first time unambiguous assignments of the intermolecular high-frequency out-of-plane and low-frequency in-plane donor OH librational modes for mixed alcohol-water complexes. The vibrational assignments confirm directly that water acts as the hydrogen bond donor in the most stable mixed complexes and the tertiary alcohol is a superior hydrogen bond acceptor. The class of large-amplitude donor OH librational motion is shown to account for up to 5.1 kJ mol(-1) of the destabilizing change of vibrational zero-point energy upon intermolecular OH center dot center dot center dot O hydrogen bond formation. The experimental findings are supported by complementary electronic structure calculations at the CCSD(T)-F12/aug-cc-pVTZ level of theory. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/8071050
- author
- Andersen, J. ; Heimdal, Jimmy LU and Larsen, R. Wugt
- organization
- publishing date
- 2015
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Physical Chemistry Chemical Physics
- volume
- 17
- issue
- 37
- pages
- 23761 - 23769
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000361543200010
- scopus:84941924850
- pmid:26304774
- ISSN
- 1463-9084
- DOI
- 10.1039/c5cp04321b
- language
- English
- LU publication?
- yes
- id
- af738906-bcf0-4089-a647-730fd7daa64d (old id 8071050)
- date added to LUP
- 2016-04-01 13:44:29
- date last changed
- 2022-04-14 02:48:52
@article{af738906-bcf0-4089-a647-730fd7daa64d,
abstract = {{The far-infrared absorption spectra have been recorded for hydrogen-bonded complexes of water with methanol and t-butanol embedded in cryogenic neon matrices at 2.8 K. The partial isotopic substitution of individual subunits enabled by a dual inlet deposition procedure provides for the first time unambiguous assignments of the intermolecular high-frequency out-of-plane and low-frequency in-plane donor OH librational modes for mixed alcohol-water complexes. The vibrational assignments confirm directly that water acts as the hydrogen bond donor in the most stable mixed complexes and the tertiary alcohol is a superior hydrogen bond acceptor. The class of large-amplitude donor OH librational motion is shown to account for up to 5.1 kJ mol(-1) of the destabilizing change of vibrational zero-point energy upon intermolecular OH center dot center dot center dot O hydrogen bond formation. The experimental findings are supported by complementary electronic structure calculations at the CCSD(T)-F12/aug-cc-pVTZ level of theory.}},
author = {{Andersen, J. and Heimdal, Jimmy and Larsen, R. Wugt}},
issn = {{1463-9084}},
language = {{eng}},
number = {{37}},
pages = {{23761--23769}},
publisher = {{Royal Society of Chemistry}},
series = {{Physical Chemistry Chemical Physics}},
title = {{The influence of large-amplitude librational motion on the hydrogen bond energy for alcohol-water complexes}},
url = {{http://dx.doi.org/10.1039/c5cp04321b}},
doi = {{10.1039/c5cp04321b}},
volume = {{17}},
year = {{2015}},
}