| 1. |
- Feyer, Vitaliy, et al.
(författare)
-
Tautomerism in Cytosine and Uracil : An Experimental and Theoretical Core Level Spectroscopic Study
- 2009
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 113:19, s. 5736-5742
-
Tidskriftsartikel (refereegranskat)abstract
- The O, N, and C 1s core level photoemission spectra of the nucleobases cytosine and uracil have been measured in the vapor phase, and the results have been interpreted via theoretical calculations. Our calculations accurately predict the relative binding energies of the core level features observed in the experimental photoemission results and provide a full assignment. In agreement with previous work, a single tautomer of uracil is populated at 405 K, giving rise to relatively simple spectra. At 450 K, three tautomers of cytosine, one of which may consist of two rotamers, are identified, and their populations are determined. This resolves inconsistencies between recent laser studies of this molecule in which the rare imino-oxo tautomer was not observed and older microwave spectra in which it was reported.
|
|
| 2. |
- Hodecker, Manuel, et al.
(författare)
-
Theoretical analysis and comparison of unitary coupled-cluster and algebraic-diagrammatic construction methods for ionization
- 2022
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 156:7
-
Tidskriftsartikel (refereegranskat)abstract
- This article describes a novel approach for the calculation of ionization potentials (IPs), or, more generally, electron-detachment energies, based on a unitary coupled-cluster (UCC) parameterization of the ground-state wave function. Explicit working equations for a scheme referred to as IP-UCC3 are given, providing electron-detachment energies and spectroscopic amplitudes of electron-detached states dominated by one-hole excitations correct through third order. In the derivation, an expansion of the UCC transformed Hamiltonian involving Bernoulli numbers as expansion coefficients is employed. Both the secular matrix and the effective transition moments are shown to be essentially equivalent to the strict third-order algebraic-diagrammatic construction scheme for the electron propagator (IP-ADC). Interestingly, due to the Bernoulli expansion, neglecting triple substitutions in the UCC expansion manifold does not affect the third-order consistency of the IP-UCC effective transition moments. Finally, the equivalence between ADC and UCC excited-state schemes is shown to not hold in fourth or higher order due to a different treatment of the correlated excited-state basis.
|
|
| 3. |
- Plekan, Oksana, et al.
(författare)
-
An Experimental and Theoretical Core-Level Study of Tautomerism in Guanine
- 2009
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 113:33, s. 9376-9385
-
Tidskriftsartikel (refereegranskat)abstract
- The core level photoemission and near edge X-ray photoabsorption spectra of guanine in the gas phase have been measured and the results interpreted with the aid of high level ab initio calculations. Tautomers are clearly identified spectroscopically, and their relative free energies and Boltzmann populations at the temperature of the experiment (600 K) have been calculated and compared with the experimental results and with previous calculations. We obtain good agreement between experiment and the Boltzmann weighted theoretical photoemission spectra, which allows a quantitative determination of the ratio of oxo to hydroxy tautomer populations. For the photoabsorption spectra, good agreement is found for the C 1s and I 1s spectra but only fair agreement for the N 1s edge.
|
|
