On the structure of the matrix isolated water trimer.
(2011) In Journal of Chemical Physics 134(6). Abstract
 Infrared spectra of partially deuterated water trimers have been investigated. It is found that HDO(H(2)O)(2) has a single, bound OD stretching fundamental, (HDO)(2)H(2)O two bound OD stretches. (HDO)(3) has a single, bound OD stretch and (H(2)O)(3) has a pair of bound OH stretches. Ab initio and discrete Fourier transform (DFT) calculations predict that the water trimer has C(1) symmetry with six different, isoenergetic minima. These calculations consequently give three numerically different OD stretches for HDO(H(2)O)(2), six for (HDO)(2)H(2)O, three for (HDO)(3), and three bound OH stretches for (H(2)O)(3). The connection between the observations and the pseudorotation of the trimer is discussed with the help of Wales' pseudorotation... (More)
 Infrared spectra of partially deuterated water trimers have been investigated. It is found that HDO(H(2)O)(2) has a single, bound OD stretching fundamental, (HDO)(2)H(2)O two bound OD stretches. (HDO)(3) has a single, bound OD stretch and (H(2)O)(3) has a pair of bound OH stretches. Ab initio and discrete Fourier transform (DFT) calculations predict that the water trimer has C(1) symmetry with six different, isoenergetic minima. These calculations consequently give three numerically different OD stretches for HDO(H(2)O)(2), six for (HDO)(2)H(2)O, three for (HDO)(3), and three bound OH stretches for (H(2)O)(3). The connection between the observations and the pseudorotation of the trimer is discussed with the help of Wales' pseudorotation model. It is found that pseudorotation is sufficiently fast to average the effective symmetry of the A(3) trimer to C(3h) and to eliminate the difference between the different ab initio minima for A(2)B. The only exception is (H(2)O)(3) where the splitting between the different bound OH stretches is largest. Here a doublet is observed due to incomplete averaging. DFT calculations indicate that the Dbonded form of HDO(H(2)O)(2) is between 50 and 60 cm(1) more stable than the Hbonded form. The energy difference is determined by differences in zero point vibration energy of intermolecular librations of the two forms. Attempts to measure the energy difference indicate that the energy difference is larger, of the order of 100 cm(1). (Less)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/record/1831820
 author
 Ceponkus, J; Uvdal, Per ^{LU} and Nelander, Bengt ^{LU}
 organization
 publishing date
 2011
 type
 Contribution to journal
 publication status
 published
 subject
 in
 Journal of Chemical Physics
 volume
 134
 issue
 6
 publisher
 American Institute of Physics
 external identifiers

 wos:000287327400029
 pmid:21322682
 scopus:79951787856
 ISSN
 00219606
 DOI
 10.1063/1.3551622
 language
 English
 LU publication?
 yes
 id
 847d48ce673d4461bedf8379c28b7e96 (old id 1831820)
 date added to LUP
 20110303 17:37:40
 date last changed
 20170730 03:04:45
@article{847d48ce673d4461bedf8379c28b7e96, abstract = {Infrared spectra of partially deuterated water trimers have been investigated. It is found that HDO(H(2)O)(2) has a single, bound OD stretching fundamental, (HDO)(2)H(2)O two bound OD stretches. (HDO)(3) has a single, bound OD stretch and (H(2)O)(3) has a pair of bound OH stretches. Ab initio and discrete Fourier transform (DFT) calculations predict that the water trimer has C(1) symmetry with six different, isoenergetic minima. These calculations consequently give three numerically different OD stretches for HDO(H(2)O)(2), six for (HDO)(2)H(2)O, three for (HDO)(3), and three bound OH stretches for (H(2)O)(3). The connection between the observations and the pseudorotation of the trimer is discussed with the help of Wales' pseudorotation model. It is found that pseudorotation is sufficiently fast to average the effective symmetry of the A(3) trimer to C(3h) and to eliminate the difference between the different ab initio minima for A(2)B. The only exception is (H(2)O)(3) where the splitting between the different bound OH stretches is largest. Here a doublet is observed due to incomplete averaging. DFT calculations indicate that the Dbonded form of HDO(H(2)O)(2) is between 50 and 60 cm(1) more stable than the Hbonded form. The energy difference is determined by differences in zero point vibration energy of intermolecular librations of the two forms. Attempts to measure the energy difference indicate that the energy difference is larger, of the order of 100 cm(1).}, articleno = {064309}, author = {Ceponkus, J and Uvdal, Per and Nelander, Bengt}, issn = {00219606}, language = {eng}, number = {6}, publisher = {American Institute of Physics}, series = {Journal of Chemical Physics}, title = {On the structure of the matrix isolated water trimer.}, url = {http://dx.doi.org/10.1063/1.3551622}, volume = {134}, year = {2011}, }