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The influence of large-amplitude librational motion on the hydrogen bond energy for alcohol-water complexes

Andersen, J.; Heimdal, Jimmy LU and Larsen, R. Wugt (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)
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author
organization
publishing date
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
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
2015-10-22 08:32:25
date last changed
2017-07-23 04:11:06
@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},
  volume       = {17},
  year         = {2015},
}