Molecular equilibrium structures from experimental rotational constants and calculated vibration–rotation interaction constants
10.1063/1.1459782
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

A detailed study is carried out of the accuracy of molecular equilibrium geometries obtained from least-squares fits involving experimental rotational constants B0 and sums of ab initio vibration–rotation interaction constants αrB. The vibration–rotation interaction constants have been calculated for 18 single-configuration dominated molecules containing hydrogen and first-row atoms at various standard levels of ab initio theory. Comparisons with the experimental data and tests for the internal consistency of the calculations show that the equilibrium structures generated using Hartree–Fock vibration–rotation interaction constants have an accuracy similar to that obtained by a direct minimization of the CCSD(T) energy. The most accurate vibration–rotation interaction constants are those calculated at the CCSD(T)/cc-pVQZ level. The equilibrium bond distances determined from these interaction constants have relative errors of 0.02%–0.06%, surpassing the accuracy obtainable either by purely experimental techniques (except for the smallest systems such as diatomics) or by ab initio methods.

Bibliography

Pawłowski, F., Jørgensen, P., Olsen, J., Hegelund, F., Helgaker, T., Gauss, J., Bak, K. L., & Stanton, J. F. (2002). Molecular equilibrium structures from experimental rotational constants and calculated vibration–rotation interaction constants. The Journal of Chemical Physics, 116(15), 6482–6496.

Authors 8
  1. Filip Pawłowski (first)
  2. Poul Jørgensen (additional)
  3. Jeppe Olsen (additional)
  4. Flemming Hegelund (additional)
  5. Trygve Helgaker (additional)
  6. Jürgen Gauss (additional)
  7. Keld L. Bak (additional)
  8. John F. Stanton (additional)
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Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 10:18 a.m.)
Deposited 1 year, 6 months ago (Feb. 6, 2024, 2:53 a.m.)
Indexed 1 month, 3 weeks ago (July 8, 2025, 6:26 a.m.)
Issued 23 years, 4 months ago (April 15, 2002)
Published 23 years, 4 months ago (April 15, 2002)
Published Print 23 years, 4 months ago (April 15, 2002)
Funders 0

None

@article{Paw_owski_2002, title={Molecular equilibrium structures from experimental rotational constants and calculated vibration–rotation interaction constants}, volume={116}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1459782}, DOI={10.1063/1.1459782}, number={15}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Pawłowski, Filip and Jørgensen, Poul and Olsen, Jeppe and Hegelund, Flemming and Helgaker, Trygve and Gauss, Jürgen and Bak, Keld L. and Stanton, John F.}, year={2002}, month=apr, pages={6482–6496} }