Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Images of desire : cognitive models of craving

Cognitive modelling of phenomena in clinical practice allows the operationalisation of otherwise diffuse descriptive terms such as craving or flashbacks. This supports the empirical investigation of the clinical phenomena and the development of targeted treatment interventions. This paper focuses on the cognitive processes underpinning craving, which is recognised as a motivating experience in substance dependence. We use a high-level cognitive architecture, Interacting Cognitive Subsystems (ICS), to compare two theories of craving: Tiffany's theory, centred on the control of automated action schemata, and our own Elaborated Intrusion theory of craving. Data from a questionnaire study of the subjective aspects of everyday desires experienced by a large non-clinical population are presented. Both the data and the high-level modelling support the central claim of the Elaborated Intrusion theory that imagery is a key element of craving, providing the subjective experience and mediating much of the associated disruption of concurrent cognition.