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Calculation Of Diagonal Born-Oppenheimer Corrections

Corrections for making the Born-Oppenheimer approximations in the quantum chemical treatment of atoms and molecules are easily computed using perturbation theory. The lowest-order correction is obtained in first-order and takes the form

\Delta E_{DBOC} = \langle \Psi_{el} | \sum_A - \frac{\hbar^2}{2 M_A} \nabla_A^2 | \Psi_{el}\rangle

This correction is known as the diabatic Born-Oppenheimer correction (DBOC) and its inclusion leads to the so-called adiabatic approximation with mass-dependent potentials that are different for the various isotopologues of a molecule.

theoretical details to DBOC corrections

implementational details to DBOC corrections

The DBOC is calculated by simply invoking the keyword

DBOC=ON

Note that CFOUR calculates the DBOC using nuclear masses.

Note that DBOC can be computed at the HF-SCF, MP1, MP2 as well as the CCSD level for both RHF and UHF reference functions. ROHF may only be used at the HF-SCF level.

Note that geometry optimizations including DBOC can be carried out using numerically evaluated gradients via METHOD=ENERONLY.

Examples

calculation of DBOC

geometry optimizations including DBOC

calculation of DBOC using non-standard isotopomers

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Page last modified on January 10, 2013, at 06:00 PM
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CFOUR is partially supported by the U.S. National Science Foundation.