6533b835fe1ef96bd129ecb8
RESEARCH PRODUCT
A combined theoretical and experimental determination of the electronic spectrum of acetone
Xing XingRuth McdiarmidManuela MerchánBjörn O. Roossubject
Photoacoustic SpectroscopyOvertoneAb initioGeneral Physics and AstronomyPhotoionizationPhotoionizationSpectral lineAcetoneBond LengthsGround Statessymbols.namesakeRydberg StatesAb initio quantum chemistry methodsPolarizationIonizationPhysics::Atomic PhysicsPhysical and Theoretical Chemistry:FÍSICA::Química física [UNESCO]Carbon MonoxideEnergyChemistryUNESCO::FÍSICA::Química físicaSurfacesBond lengthElectron SpectraRydberg formulasymbolsAb Initio Calculations ; Acetone ; Bond Lengths ; Carbon Monoxide ; Electron Spectra ; Energy ; Ground States ; Multi−Photon Processes ; Photoacoustic Spectroscopy ; Photoionization ; Polarization ; Rydberg States ; SurfacesMulti−Photon ProcessesAtomic physicsAb Initio Calculationsdescription
A combined ab initio and experimental investigation has been performed of the main features of the electronic spectrum of acetone. Vertical transition energies have been calculated from the ground to the ny→π∗, π→π∗, σ→π∗, and the n=3 Rydberg states. In addition, the 1A1 energy surfaces have been studied as functions of the CO bond length. The 1A1 3p and 3d states were found to be heavily perturbed by the π→π∗ state. Resonant multiphoton ionization and polarization‐selected photoacoustic spectra of acetone have been measured and observed transitions were assigned on internal criteria. The calculated vertical transition energies to the ny→π∗ and all Rydberg states were found to be in agreement with experiment. This includes the 3s‐, all three 3p‐, and the A1, B1, and B2 3d‐Rydberg states. By contrast, there is little agreement between the calculated and experimental relative intensities of the A1 and B2 3d‐Rydberg transitions. In addition, anomalously intense high vibrational overtone bands of one of the 3p‐Rydberg transitions have been observed. These results confirm the strong perturbation of the 3p‐ and 3d‐Rydberg states by the π→π∗ state found in the theoretical calculation and support the calculated position of this unobserved state. merchan@uv.es
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1996-02-01 | The Journal of Chemical Physics |