Atomization energies at 0 K and heats of formation at 298 K were obtained for a collection of small halogenated molecules from coupled cluster theory including noniterative, quasiperturbative triple excitations calculations with large basis sets (up through augmented septuple zeta quality in some cases). In order to achieve near chemical accuracy (±1 kcal/mol) in the thermodynamic properties, we adopted a composite theoretical approach which incorporated estimated complete basis set binding energies based on frozen core coupled cluster theory energies and (up to) five corrections: (1) a core/valence correction; (2) a Douglas–Kroll–Hess scalar relativistic correction; (3) a first-order atomic spin–orbit correction; (4) a second-order spin–orbit correction for heavy elements; and (5) an approximate correction to account for the remaining correlation energy. The last of these corrections is based on a recently proposed approximation to full configuration interaction via a continued fraction approximant for coupled cluster theory [CCSD(T)-cf]. Failure to consider corrections (1) to (4) can introduce errors significantly in excess of the target accuracy of ±1 kcal/mol. Although some cancellation of error may occur if one or more of these corrections is omitted, such a situation is by no means universal and cannot be relied upon for high accuracy. The accuracy of the Douglas–Kroll–Hess approach was calibrated against both new and previously published four-component Dirac Coulomb results at the coupled cluster level of theory. In addition, vibrational zero-point energies were computed at the coupled cluster level of theory for those polyatomic systems lacking an experimental anharmonic value.
Skip Nav Destination
Article navigation
22 February 2003
Research Article|
February 04 2003
Performance of coupled cluster theory in thermochemical calculations of small halogenated compounds
David Feller;
David Feller
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-91, Richland, Washington 99352
Search for other works by this author on:
Kirk A. Peterson;
Kirk A. Peterson
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-91, Richland, Washington 99352
Search for other works by this author on:
Wibe A. de Jong;
Wibe A. de Jong
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-91, Richland, Washington 99352
Search for other works by this author on:
David A. Dixon
David A. Dixon
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-91, Richland, Washington 99352
Search for other works by this author on:
J. Chem. Phys. 118, 3510–3522 (2003)
Article history
Received:
September 25 2002
Accepted:
November 01 2002
Citation
David Feller, Kirk A. Peterson, Wibe A. de Jong, David A. Dixon; Performance of coupled cluster theory in thermochemical calculations of small halogenated compounds. J. Chem. Phys. 22 February 2003; 118 (8): 3510–3522. https://doi.org/10.1063/1.1532314
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00