On malonaldehyde and acetylacetone: are theory and experiment compatible?

Bauer, S. H.; Wilcox, Charles F.

doi:10.1016/s0009-2614(97)01024-5

Cited by 55 publications

(48 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[5][6][7] Among the class of chemical reactions, proton-transfer processes are of prime importance in chemistry and biochemistry (ref. [19][20][21][22][23][24][25][26] In this article we investigate the mechanism of keto-enol tautomerism in the gas-phase acetylacetone (Pentane-2,4-dione) molecule. Keto-enol tautomerism is a prototype of such processes which has been, and is still, widely investigated.…”

Section: Introductionmentioning

confidence: 99%

Probing keto–enol tautomerism using photoelectron spectroscopy

Capron

Casier

Sisourat

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest transition state as well as several intermediate geometries between the two stable tautomers have been identified. The outer-valence ionization spectra for all determined geometries have been computed using the third-order non-Dyson algebraic diagrammatic construction technique. Furthermore, the oxygen core-shell ionization spectra for these geometries have been obtained using DFT and the Becke three-parameter Lee-Yang-Parr (B3LYP) functional. It is shown that all spectra depend strongly on the geometries demonstrating the possibility of following the proton-transfer dynamics using photoelectron spectroscopy in pump-probe experiments.

show abstract

Section: Introductionmentioning

confidence: 99%

Probing keto–enol tautomerism using photoelectron spectroscopy

Capron

Casier

Sisourat

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…It should be noted that work allowing a direct comparison of the two molecules, i.e. using same experimental or theoretical methods, are a very few [39][40][41].…”

Section: Introductionmentioning

confidence: 99%

Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices

Trivella¹,

Coussan²,

Chiavassa³

et al. 2006

Low Temperature Physics

View full text Add to dashboard Cite

Structure and reactivity of the eight enolic forms (one chelated and seven non-chelated) of malonaldehyde and acetylacetone are compared through theoretical and experimental data. Ground-state geometries, energies, and vibrational frequencies are calculated with the B3LYP/6-311++G(2d,2p) model chemistry. The electronic delocalisation as well as the cis/trans rotamer properties are analysed. The hydrogen bond strength of the chelated forms can be estimated by the energy difference between chelated and non-chelated forms, and its enhancement due to methyl-induced electron release is estimated at 1.7 kcal·mol -1 . UV-and IR-induced reactivity of molecules isolated in nitrogen matrices is studied by means of FT-IR spectrometry. Interconversion between rotamers is the main process observed for both molecules, only some among the seven non-chelated forms being created.PACS: 36.20.Ng, 31.15.Ar

show abstract

“…66,67 Comparison with the first row of Table IV suggests the CCSD methods are particularly accurate for this quantity. Averaging of thermochemical properties for the closely related acetylacetone 68 yield a similar value of 4 kcal/mol. The measurements of the excited states of malonaldehyde consist largely of tunneling splitting data.…”

Section: Comparison With Past Workmentioning

confidence: 76%

Comparison of methods for calculating the properties of intramolecular hydrogen bonds. Excited state proton transfer

Kar

Scheiner

C̆uma

1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

A series of molecules related to malonaldehyde, containing an intramolecular H-bond, are used as the testbed for a variety of levels of ab initio calculation. Of particular interest are the excitation energies of the first set of valence excited states, n* and *, both singlet and triplet, as well as the energetics of proton transfer in each state. Taking coupled cluster results as a point of reference, configuration interaction-singles-second-order Møller-Plesset ͑CIS-MP2͒ excitation energies are too large, as are CIS to a lesser extent, although these approaches successfully reproduce the order of the various states. The same may be said of complete active space self-consistent-field ͑CASSCF͒, which is surprisingly sensitive to the particular choice of orbitals included in the active space. Complete active space-second-order perturbation theory ͑CASPT2͒ excitation energies are rather close to coupled cluster singles and doubles ͑CCSD͒, as are density functional theory ͑DFT͒ values. CASSCF proton transfer barriers are large overestimates; the same is true of CIS to a lesser extent. MP2, CASPT2, and DFT barriers are closer to coupled cluster results, although yielding slight underestimates.

show abstract

On malonaldehyde and acetylacetone: are theory and experiment compatible?

Cited by 55 publications

References 28 publications

Probing keto–enol tautomerism using photoelectron spectroscopy

Probing keto–enol tautomerism using photoelectron spectroscopy

Comparative study of structure and photo-induced reactivity of malonaldehyde and acetylacetone isolated in nitrogen matrices

Comparison of methods for calculating the properties of intramolecular hydrogen bonds. Excited state proton transfer

Contact Info

Product

Resources

About