6533b7dcfe1ef96bd1272b71
RESEARCH PRODUCT
Quantum-chemical determination of Born–Oppenheimer breakdown parameters for rotational constants: the open-shell species CN, CO+ and BO
Jürgen GaussCristina Puzzarinisubject
AB INITIO CALCULATIONSChemistryBorn–Huang approximationBiophysicsBorn–Oppenheimer approximationRotational transitionRotational temperatureCondensed Matter PhysicsROTATIONAL CONSTANTSDiatomic moleculesymbols.namesakesymbolsBorn-Oppenheimer breakdown correctionRotational spectroscopyPhysics::Chemical PhysicsPhysical and Theoretical ChemistryAtomic physicsRotational partition functionMolecular BiologyOpen shelldescription
The quantum-chemical protocol for computing Born-Oppenheimer breakdown corrections to rotational constants in the case of diatomic molecules is extended to open-shell species. The deviation from the Born-Oppenheimer equilibrium rotational constant is obtained by considering three contributions: the adiabatic correction to the equilibrium bond distance, the electronic contribution to the moment of inertia requiring the computation of the rotational g-tensor, and the so-called Dunham correction. Values for the Born-Oppenheimer breakdown parameters of CN, CO+, and BO in their (2)sigma(+) electronic ground states are reported based on coupled-cluster calculations of the involved quantities and compared to available experimental data.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2013-05-30 | Molecular Physics |