Transition structures for the interchange of hydrogen atoms within the water dimer
10.1063/1.458133
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

High levels of ab initio molecular orbital theory were used to examine rearrangement processes in the water dimer corresponding to the interchange of various hydrogen atoms. Our most reliable calculations involve MP4/6-311+G(2df,2p) energy evaluations at MP2/6-311+G(d,p) optimized structures. The lowest energy rearrangement pathway corresponds to the interchange of hydrogen atoms of the acceptor molecule within the Cs water dimer structure (1). This proceeds via a transition structure of C1 symmetry (2) and requires an energy of 0.59 kcal mol−1. The interchange of donor and acceptor molecules can be achieved via a transition structure with Ci symmetry (4) and requires an energy of 0.87 kcal mol−1. Finally, the interchange of hydrogen atoms of the donor molecule, via a C2v transition structure (9), requires 1.88 kcal mol−1. The rearrangements via 2 and 4 lead to complete scrambling of hydrogen atoms within the individual H2O moieties at a cost of 0.87 kcal mol−1; the transition structure 9 is not necessary for this process. The implications of these results with regard to the interpretation of spectroscopic data on the water dimer will be of interest.

Bibliography

Smith, B. J., Swanton, D. J., Pople, J. A., Schaefer, H. F., & Radom, L. (1990). Transition structures for the interchange of hydrogen atoms within the water dimer. The Journal of Chemical Physics, 92(2), 1240–1247.

Authors 5
  1. Brian J. Smith (first)
  2. David J. Swanton (additional)
  3. John A. Pople (additional)
  4. Henry F. Schaefer (additional)
  5. Leo Radom (additional)
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Dates
Type When
Created 23 years ago (July 26, 2002, 9:12 a.m.)
Deposited 1 year, 6 months ago (Feb. 10, 2024, 6:11 a.m.)
Indexed 2 months, 1 week ago (June 12, 2025, 3:50 a.m.)
Issued 35 years, 7 months ago (Jan. 15, 1990)
Published 35 years, 7 months ago (Jan. 15, 1990)
Published Print 35 years, 7 months ago (Jan. 15, 1990)
Funders 0

None

@article{Smith_1990, title={Transition structures for the interchange of hydrogen atoms within the water dimer}, volume={92}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.458133}, DOI={10.1063/1.458133}, number={2}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Smith, Brian J. and Swanton, David J. and Pople, John A. and Schaefer, Henry F. and Radom, Leo}, year={1990}, month=jan, pages={1240–1247} }