| 1. |
- Andersson, Kerstin, 1961-
(författare)
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Molecular properties of TCNQ and anions
- 2023
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Ingår i: Theoretical Chemistry accounts. - : Springer. - 1432-881X .- 1432-2234. ; 142:6
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Tidskriftsartikel (refereegranskat)abstract
- The purpose of the work is to calculate accurate values of molecular properties of tetracyanoquinodimethane (TCNQ) and anions using the complete active space self-consistent field and complete active space second-order perturbation theory methods. The accuracy has been evaluated using several basis sets and active spaces. The calculated properties have, in many cases, been confirmed by experimental data (within parentheses), e.g., 9.54 eV (9.61 eV) and 3.36 eV (3.38 eV) for the ionization potential and electron affinity, respectively, of TCNQ; 3.12 eV (3.01 eV) and 3.54 eV (3.42 or 3.60 eV) for transition energies to the two lowest-lying excited singlet states of TCNQ; − 0.03, 0.46 and 1.44 eV (0, 0.5 and 1.4 eV) for electronic energies in electron attachment of TCNQ forming $$\hbox {TCNQ}^-$$; and 3.88 eV (3.71 eV) for the transition energy to the second lowest-lying excited singlet state of $$\hbox {TCNQ}^{2-}$$. Further, the calculations have brought insight into some experimental observations, e.g., the shape of the fluorescence spectrum of TCNQ at 3–4 eV.
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| 2. |
- Pettersson, Lars G. M., et al.
(författare)
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X-ray emission spectroscopy : a genetic algorithm to disentangle core-hole-induced dynamics
- 2021
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Ingår i: Theoretical Chemistry accounts. - : Springer Science and Business Media LLC. - 1432-881X .- 1432-2234. ; 140:12
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Tidskriftsartikel (refereegranskat)abstract
- A genetic algorithm (GA) is developed and applied to make proper connections of final-state potential-energy surfaces and X-ray emission (XES) cross sections between steps in the time-propagation of H-bonded systems after a core–hole is created. We show that this modification results in significantly improved resolution of spectral features in XES with the semiclassical Kramers–Heisenberg approach which takes into account important interference effects. We demonstrate the effects on a water pentamer model as well as on two 17-molecules water clusters representing, respectively, tetrahedral (D2A2) and asymmetric (D1A1) H-bonding environments. For D2A2, the applied procedure improves significantly the obtained intensities, whereas for D1A1 the effects are smaller due to milder dynamics during the core–hole life-time as only one hydrogen is involved. We reinvestigate XES for liquid ethanol and, by properly disentangling the relevant states in the dense manifold of states using the GA, now resolve the important 3a′′ state as a peak rather than a shoulder. Furthermore, by applying the SpecSwap-RMC procedure, we reweigh the distribution of structures in the sampling of the liquid to fit to experiment and estimate the ratio between the main anti and gauche conformers in the liquid at room temperature. This combination of techniques will be generally applicable to challenging problems in liquid-phase spectroscopy.
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| 3. |
- Velasco-Juarez, Elena, et al.
(författare)
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A novel partitioning scheme for the application of the distortion/interaction - activation strain model to intramolecular reactions
- 2021
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Ingår i: Theoretical Chemistry accounts. - : Springer. - 1432-881X .- 1432-2234. ; 140:8
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Tidskriftsartikel (refereegranskat)abstract
- The distortion/interaction or activation strain model, developed by Houk and Bickelhaupt, relates chemical reactivity to the reagents deformations and reciprocal electronic influences. However, in its original formulation, it struggles to elucidate the mechanistic insights of intramolecular reactions, those unimolecular processes in which two parts of a molecule, the reaction centers, linked by a connector, are brought together to yield a different chemical species. Here we present a modification of the distortion/interaction procedure for its application on intramolecular reactions. This new procedure allows the calculation of the influence exerted by the connector over the reaction pathway in an indirect way, from the distortions of the two reaction centers and their interaction energy. This procedure does not include additional, undesired interactions and offers the possibility of calculating very large connectors in a computationally inexpensive way. We applied this methodology in the normal electron-demand Diels-Alder reaction of 1,3,8-nonatriene derivatives, with different functionalizations and connector lengths. In-depth analysis of the IRC showed that the reaction pathway can be subdivided in three main regions, what we called the oncoming, conversion and relaxation phases, each of them characterized by different evolutions of the distortion and interaction energies, and with clear geometry changes. We suggest that this new formulation can provide additional information for intramolecular reactions, especially to those processes for which the connector is said to play a crucial role in the observed reaction rates.
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| 4. |
- Yannacone, Seth F., et al.
(författare)
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Quantitative assessment of intramolecular hydrogen bonds in neutral histidine
- 2020
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Ingår i: Theoretical Chemistry accounts. - : Springer Science and Business Media LLC. - 1432-881X .- 1432-2234. ; 139:7
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Tidskriftsartikel (refereegranskat)abstract
- Experimentalists recently characterized the difficulty in isolating gaseous histidine in its neutral form. To understand the factors which stabilize neutral histidine, the intrinsic nature of the intramolecular hydrogen bonding networks in the four most stable histidine conformers was investigated via density functional theory combined with the local vibrational mode analysis originally introduced by Konkoli and Cremer, quantum theory of atoms in molecules, non-covalent interaction analysis, and natural bond orbital population analysis. Our results show a positive correlation between intramolecular hydrogen bond strength and structural stability, where the presence of the O−H⋯Nα bond type is a major factor.
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