Targeted Public Distribution System in Food Grains:Extent of Utlization by the Tribal Population in Kerala

In India, Food Security meant supply of food grains and the medium was Public Distribution System. Public Distribution System (PDS) is a rationing mechanism that entitles households to specified quantities of selected commodities at subsidized prices. The Objectives of PDS are maintaining Price Stability, rationing during times of scarcity, welfare of the poor, and keeping a check on private trade. Kerala has registered remarkable improvement in poverty reduction in general over the years among all social sections, including scheduled caste and scheduled tribe population. As part of the structural adjustment intended to reduce public expenditure, PDS has been modified as Revamped PDS (RPDS) during 1992 and later on as Targeted PDS (TPDS) in 1997, intended to target households on the basis of income criterion, classifying people as Below Poverty Line (BPL) and Above Poverty Line (APL). TPDS provides 25Kg. of food gra.ins through the Fair Price Shops per month @ Rs.3/- per Kg. of rice/ wheat to the BPL category and @Rs.8.90 and Rs.6.7O for rice and wheat respectively to the APL category of people. Since TPDS is intended to target the poor people, the subsidy spent by the government for the scheme should be beneficial to the poor people and naturally they should utilize the benefits by purchasing the food grains allotted under the scheme. Several studies have shown that there is underutilization of the allotments under TPDS. Therefore, the extent of utilization of TPDS in food grains, how and why remains as a major hurdle, in improving the structure and system of PDS. Livelihood of the tribal population being under threat due to increasing degradation of the resources, the targeting system ought to be effective among the tribal population. Therefore, performance of the TPDS in food grains, in terms of the utilization by the tribal population in Kerala, impact thereof and the factors, if any, affecting proper utilization were considered as the research problem in this study. The study concentrated on the pattern of consumption of food grains by the tribal people, whether their hunger needs are met by distribution of food grains through the TPDS, extent to which TPDS in food grains reduce their share of expenditure on food in the total household expenditure, and the factors affecting the utilization of the TPDS in food grains by the tribal population. Going through the literature, it has been noted that only few studies concentrated on the utilization of TPDS in food grains among the tribal population in Kerala.The Research Design used in this study is descriptive in nature, but exploratory in some aspects. Idukki, Palakkad and Wayanad have more than 60% of the population of the tribals in the state. Within the three districts mentioned above, 14 villages with scheduled tribe concentration were selected for the study. 95 tribal colonies were selected from among the various tribal settlements. Collection of primary data was made from 1231 households with in the above tribal colonies. Analysis of data on the socio-economic factors of the tribal people, pattern of food consumption, extent of reduction in the share of expenditure on food among the household expenditure of the tribal people and the impact of TPDS on the tribal families etc. and testing of hypotheses to find out the relation/association of each of the six variables, using the data on BPL and APL categories of households separately have resulted in findings such as six percent of the tribal families do not have Ration Cards, average per capita consumption of food grains by the tribal people utilizing TPDS meets 62% of their minimum requirement, whereas the per capita consumption of food grains by the tribal people is higher than the national average per capita consumption, 63% deficiency in food grains may be felt by tribal people in general, if TPDS is withdrawn, and the deficit for BPL tribal people may be 82%, TPDS facilitates a reduction of 9.71% in the food expenditure among the total household expenditure of the tribal people in general, share of food to non-food among BPL category of tribals is 55:45 and 40:60 among the APL, Variables, viz. household income, number of members in the family and distance of FPS from tribal settlements etc. have influence on the quantity of rice being purchased by the tribal people from the Fair Price Shops, and there is influence of household income and distance of FPS from tribal settlements on the quantity of rice being purchased by the tribal people from the open market. Rationing with differential pricing on phased allotments, rectification of errors in targeting, anomalies in norms and procedures for classifying tribal people as BPL/APL, exclusive Income Generation for tribal population, paddy cultivation in the landholdings possessed by the tribal people, special drive for allotment of Ration Cards to the tribal people, especially those belonging to the BPL category, Mobile Fair Price Shops in tribal settlements, ensure quality of the food grains distributed through the TPDS, distribution of wheat flour in packed condition instead of wheat through the Fair Price Shops are recommended to address the shortcomings and weaknesses of the TPDS vis-avis the tribal population in Kerala.

Studies on the macrobenthos of mudbanks of Southwest cost of India

The present study was undsrtaken.with the objectives to assess the distribution and density of population of benthic animals with special reference to macrofauna from the south west coast of India from ' Malippursa 1 in the north to Alleppey in the south, to evaluate significant difference, if any, in the number and distribution of animals in th md bank regions and other intermittent stations, to examine the influence of bottom stability on the distribution of fauna, to observe the effect of the environmental parameters on the distribution pattern of nacrofauna, and to evaluate the nature and depthpwise distribution of the benthic fishery. The region selected for the investigation is one of the nest important fishing grounds in India for bottom fishing especially for prawns, covering a distance of about 60 kns in length.total number of thirty stations in five transects at right angles to the coast, each consisting of six stations were surveyed. The six stations in a transect were at depths of 5 m, 10m, 20:, 30:, 35m and 45m respectively formation of the Iudbanke, popularly known as 'Ghaknra' in the local language, is a peculiar phenomenon along the ooaet of Kerala and provides a good fishing ground.quantitative distribution of the mecrofauna chewed that the maximum number of organism was near the 35 n contour line in the first three profiles whereas in the fourth and fifth profiles it was at 20 n and 30 m depth respectively. The density of the fauna wee comparatively poor in shallow water etatione at depths 5-‘IO M.was a general decline in the numerical abundance and biomass of the bottom fauna in all the stations during the monsoon period. There has been very little yearly change in the composition of the fauna during the two years‘ study.

Reduction of radar cross section of targets using periodic strip grating technique

The- classic: experiment of Heinrich Hertz verified the theoretical predict him of Maxwell that kxnfli radio and light waves are physical phenomena governed by the same physical laws. This has started a.rnnJ era of interest in interaction of electromagnetic energy with matter. The scattering of electromagnetic waves from a target is cleverly utilized im1 RADAR. This electronic system used tx> detect and locate objects under unfavourable conditions or obscuration that would render the unaided eye useless. It also provides a means for measuring precisely the range, or distance of an object and the speed of a moving object. when an obstacle is illuminated by electromagnetic waves, energy is dispersed in all directions. The dispersed energy depends on the size, shape and composition of the obstacle and frequency and nature of the incident wave. This distribution of energy’ is known as ‘scattering’ and the obstacle as ‘scatterer’ or 'target'.

Design and Development of Compact Chipless RFID Tags with High Data Encoding Capacity

The main objective of this thesis is to develop a compact chipless RFID tag with high data encoding capacity. The design and development of chipless RFID tag based on multiresonator and multiscatterer methods are presented first. An RFID tag using using SIR capable of 79bits is proposed. The thesis also deals with some of the properties of SIR like harmonic separation, independent control on resonant modes and the capability to change the electrical length. A chipless RFID reader working in a frequency band of 2.36GHz to 2.54GHz has been designed to show the feasibility of the RFID system. For a practical system, a new approach based on UWB Impulse Radar (UWB IR) technology is employed and the decoding methods from noisy backscattered signal are successfully demonstrated. The thesis also proposes a simple calibration procedure, which is able to decode the backscattered signal up to a distance of 80cm with 1mW output power.

Preparation and applications of periodical gold nanoparticle arrays

Diese Arbeit beschäftigt sich mit der Herstellung und Anwendungen von periodischen Goldnanopartikel-Arrays (PPAs), die mit Hilfe von Nanosphären-Lithografie hergestellt wurden. In Abhängigkeit der verwendeten Nanosphären-Größe wurden dabei entweder kleine dreieckige Nanopartikel (NP) (bei Verwendung von Nanosphären mit einem Durchmesser von 330 nm) oder große dreieckige NPD sowie leicht gestreckte NP (bei Verwendung von Nanosphären mit einem Durchmesser von 1390 nm) hergestellt. Die Charakterisierung der PPAs erfolgte mit Hilfe von Rasterkraftmikroskopie, Rasterelektronenmikroskopie und optischer Spektroskopie. Die kleinen NP besitzen ein Achsverhältnis (AV) von 2,47 (Kantenlänge des NPs: (74+/-6) nm, Höhe: (30+/-4) nm. Die großen dreieckigen NP haben ein AV von 3 (Kantenlänge des NPs:(465+/-27) nm, Höhe: (1530+/-10) nm) und die leicht gestreckten NP (die aufgrund der Ausbildung von Doppelschichten ebenfalls auf der gleichen Probe erzeugt wurden) haben eine Länge von (364+/-16)nm, eine Breite von (150+/-20) nm und eine Höhe von (150+/-10)nm. Die optischen Eigenschaften dieser NP werden durch lokalisierte Oberflächenplasmon-Polariton Resonanzen (LPPRs) dominiert, d.h. von einem eingestrahlten elektromagnetischen Feld angeregte kollektive Schwingungen der Leitungsbandelektronen. In dieser Arbeit wurden drei signifikante Herausforderungen für Plasmonik-Anwendungen bearbeitet, welche die einzigartigen optischen Eigenschaften dieser NP ausnutzen. Erstens wurden Ergebnisse der selektiven und präzisen Größenmanipulation und damit einer Kontrolle der interpartikulären Abstände von den dreieckigen Goldnanopartikel mit Hilfe von ns-gepulstem Laserlicht präsentiert. Die verwendete Methode basiert hierbei auf der Größen- und Formabhängigkeit der LPPRs der NP. Zweitens wurde die sensorischen Fähigkeiten von Gold-NP ausgenutzt, um die Bildung von molekularen Drähten auf den PPAs durch schrittweise Zugabe von unterschiedlichen molekularen Spezies zu untersuchen. Hierbei wurde die Verschiebung der LSPPR in den optischen Spektren dazu ausgenutzt, die Bildung der Nanodrähte zu überwachen. Drittens wurden Experimente vorgestellt, die sich die lokale Feldverstärkung von NP zu nutze machen, um eine hochgeordnete Nanostrukturierung von Oberflächen mittels fs-gepulstem Laserlicht zu bewerkstelligen. Dabei zeigt sich, dass neben der verwendeten Fluenz die Polarisationsrichtung des eingestrahlten Laserlichts in Bezug zu der NP-Orientierung sowie die Größe der NP äußerst wichtige Parameter für die Nanostrukturierung darstellen. So konnten z.B. Nanolöcher erzeugt werden, die bei höheren Fluenzen zu Nanogräben und Nanokanälen zusammen wuchsen. Zusammengefasst lässt sich sagen, dass die in dieser Arbeit gewonnen Ergebnisse von enormer Wichtigkeit für weitere Anwendungen sind.

Spatial and harvesting influence on growth, yield, quality and economic potential of Kalmegh (Andrographis paniculata Wall Ex. Nees)

Andrographis paniculata, commonly known as Kalmegh, is used both in Ayurvedic and Unani system of medicines because of its immunological, antibacterial and hepatoprotective properties. This study was carried out to investigate the influence of four harvesting times (120,135,150 days after planting and at seed maturity) and four planting distances (30×15, 30×10, 20×15 and 20×10 cm) on growth, dry herbage biomass, seed yield and quality traits of Andrographis paniculata at CCS Haryana Agricultural University, Hisar, India in the two years 2005 and 2006. The treatments were laid out in a split plot design with three replications. The maximum values for dry herbage biomass yield (5.14 t ha^(-1)), net returns (760.00 EUR ha^(-1)), B:C ratio (2.59), andrographolide content (2.63%) and total yield (135.00 kg ha^(-1)) were detected 135 days after planting with an optimum planting distance of 30×15 cm. However, the maximum iron content was estimated 120 days after planting. The highest dry herbage (4.58 t ha^(-1)) and maximum seed yield (19.7 kg ha^(-1)) were registered at plants that were lined out with a distance of 20×10 cm.

Um estudo sobre a relação entre os tipos motivacionais de valores e o desempenho escolar de alunos do IFAM-campus Manaus Zona Leste

O presente estudo investiga os principais tipos motivacionais de valores dos alunos que freqüentam o 1° ano no IFAM – Instituto Federal de Educação, Ciência e Tecnologia do Amazonas - Campus Manaus Zona Leste, e a relação com o desempenho escolar dos alunos. Fundamentou-se em Schwartz (2006) e Tamayo (2007) que apresentam os tipos motivacionais de valores como valores universais e organizacionais. A pesquisa tem um enfoque exploratório-descritivo já que tem o propósito de proporcionar uma visão geral acerca de determinado fato. É considerado o primeiro estágio da pesquisa, onde se conhece o objeto de estudo tal como se apresenta, os seus significados e o contexto onde se insere. A amostra compõe-se de seis turmas das primeiras séries do curso de formação técnico-profissional representadas por setenta e cinco alunos. Os dados foram obtidos através de questionários com variáveis para análise quantitativa, que descrevem as características de uma população. Para a tabulação dos dados estatísticos foi utilizado o software ABD do Windows SPSS e a planilha do EXCEL. Verificou-se que o IFAM – Campus Manaus Zona Leste representa um lugar onde os alunos dos mais longínquos locais do Amazonas e até de alguns estados vizinhos vêm em busca de conhecimentos na área de agropecuária. Na opinião dos pesquisados o espaço físico, o horário integral, as dificuldades financeiras, a distância dos familiares interferem no processo ensino aprendizagem. Da mesma forma afirmam que os tipos motivacionais que caracterizam as suas opções, interferem no desempenho escolar.

California's Endangered Belding’s Savannah Sparrow (Passerculus sandwichensis beldingi): Tolerance of Pedestrian Disturbance

Salt marshes constitute habitat islands for many endemic animal species, particularly along the California coast, where urban sprawl has fragmented this habitat. Recreational activities in salt marshes have increased recently, posing an interesting problem: how do endemic species lacking alternative habitat modify their tolerance to humans? We assessed seasonal and site variations in three tolerance parameters (distances at which animals became alert, fled, and moved after fleeing) of California's endangered Belding’s Savannah Sparrow ((Passerculus sandwichensis beldingi). We approached individuals on trails in three salt marshes with different levels of vehicle and pedestrian traffic. Belding’s Savannah Sparrows became aware and fled at shorter distances in the salt marsh coincident with greater levels of recreational activity as a result of habituation or visual obstruction effects. Seasonal effects in tolerance varied between sites. Alert and flight initiation distances were higher in the pre-nesting than in the non-breeding season in the site with the highest levels of recreational use likely due to greater exposure of breeding individuals; however, the opposite seasonal trend was found in each of the two sites with relatively lower human use, probably because individuals were less spatially attached in the non-breeding season when they foraged in aggregations. Distance fled was greater in the non-breeding than in the breeding season. Our findings call for dynamic management of recreational activities in different salt marshes depending on the degree of exposure to humans and seasonal variations in tolerance. We recommend a minimum approaching distance of 63 m and buffer areas of 1.3 ha around Belding's Savannah Sparrows.

Patterns of pollen and seed dispersal in a small, fragmented population of the wind-pollinated tree Araucaria angustifolia in southern Brazil

Paternity analysis based on eight microsatellite loci was used to investigate pollen and seed dispersal patterns of the dioecious wind- pollinated tree, Araucaria angustifolia. The study sites were a 5.4 ha isolated forest fragment and a small tree group situated 1.7 km away, located in Paran alpha State, Brazil. In the forest fragment, 121 males, 99 females, 66 seedlings and 92 juveniles were mapped and genotyped, together with 210 seeds. In the tree group, nine male and two female adults were mapped and genotyped, together with 20 seeds. Paternity analysis within the forest fragment indicated that at least 4% of the seeds, 3% of the seedlings and 7% of the juveniles were fertilized by pollen from trees in the adjacent group, and 6% of the seeds were fertilized by pollen from trees outside these stands. The average pollination distance within the forest fragment was 83 m; when the tree group was included the pollination distance was 2006m. The average number of effective pollen donors was estimated as 12.6. Mother- trees within the fragment could be assigned to all seedlings and juveniles, suggesting an absence of seed immigration. The distance of seedlings and juveniles from their assigned mother- trees ranged from 0.35 to 291m ( with an average of 83m). Significant spatial genetic structure among adult trees, seedlings, and juveniles was detected up to 50m, indicating seed dispersal over a short distance. The effective pollination neighborhood ranged from 0.4 to 3.3 ha. The results suggest that seed dispersal is restricted but that there is longdistance pollen dispersal between the forest fragment and the tree group; thus, the two stands of trees are not isolated.

Fate of prions in soil: Longevity and migration of recPrP in soil columns

Research into transmissible spongiform encephalopathy (TSE) diseases has become a high priority worldwide in recent years yet remarkably little is known about the behaviour of TSE infectivity in the environment. The resilience and stability of prion proteins could lead to soils becoming a potential reservoir of TSE infectivity as a result of contamination from activities such as infected carcass burial or the dispersion of effluents from slaughter houses, or by contamination of pastures by infected animals, (e.g. scrapie in sheep). Knowledge of the fate of prion proteins in soils, and associated physico-chemical conditions which favour migration, can be used to help prevent re-infection of animals through grazing, to protect watercourses and develop good management practices. In two consecutive experiments of 9 and 6 months, the migration of recombinant ovine PrP (recPrP) in soil columns was followed under contrasting levels of microbial activity (normal versus reduced), under varying regimes of soil water content and redox potential, and in two different soil types (loamy sand and clay loam). At each analysis time (1, 3, 6 or 9 months), in both soil types, full-length recPrP was detected in the original contaminated layer, indicating the resilience and stability of recPrP under varied soil conditions, even in the presence of active soil microbial populations. Evidence of protein migration was found in every soil column at the earliest analysis time (1 or 3 months), but was restricted to a maximum distance of 1 cm, indicative of limited initial mobility in soils followed by strong adsorption over the following days to weeks. The survival of recPrP in the soil over a period of at least 9 months was demonstrated. In this study, recPrP was used as an indicator for potential TSE infectivity, although infectivity tests should be carried out before conclusions can be drawn regarding the infection risk posed by prions in soil. However, it has been demonstrated that soil is likely to act as a significant barrier to the dispersion of contaminated material at storage or burial sites. (c) 2007 Elsevier Ltd. All rights reserved.

Adsorption of water vapor by bare soil in an olive grove in southern Spain

Data for water vapor adsorption and evaporation are presented for a bare soil (sandy loam, clay content 15%) in a southern Spanish olive grove. Water losses and gains were measured using eight high-precision minilysimeters, placed around an olive tree, which had been irrigated until the soil reached field capacity (similar to 0.22 m(3) m(-3)). They were subsequently left to dry for 10 days. A pair of lysimeters was situated at each of the main points of the compass (N, E, S, W), at a distance of 1 m (the inner set of lysimeters; ILS) and 2 m (the outer set of lysimeters; OLS), respectively, from the tree trunk. Distinct periods of moisture loss (evaporation) and moisture gain (vapor adsorption) could be distinguished for each day. Vapor adsorption often started just after noon and generally lasted until the (early) evening. Values of up to 0.7 mm of adsorbed water per day were measured. Adsorption was generally largest for the OLS (up to 100% more on a daily basis), and increased during the dry down. This was mainly the result of lower OLS surface soil moisture contents (period-average absolute difference similar to 0.005 m(3) m(-3)), as illustrated using various analyses employing a set of micrometeorological equations describing the exchange of water vapor between bare soil and the atmosphere. These analyses also showed that the amount of water vapor adsorbed by soils is very sensitive to changes in atmospheric forcing and surface variables. The use of empirical equations to estimate vapor adsorption is therefore not recommended.

Spatio-temporal analysis of an invasive plant pathogen (Phytophthora ramorum) in England and Wales

Phytophthora ramorum is a damaging invasive plant pathogen and was first discovered in the UK in 2002. Spatial point analyses were applied to the occurrence of this disease in England and Wales during the period of 2003-2006 in order to assess its spatio-temporal spread. Out of the 4301 garden centres and nurseries (GCN) surveyed, there were 164, 105, 123 and 41 sites with P. ramorum in 2003, 2004, 2005 and 2006, respectively. Spatial analysis of the observed point patterns of GCN outbreaks suggested that these sites were significantly clumped within a radius of ca 60 km in 2003, but not in later years. Further analyses were conducted to determine the relationship of GCN outbreak sites over two consecutive years and thus to infer possible disease spread over time. This analysis suggested that disease spread among GCN sites was most likely to have occurred within a distance of 60 km for 2003-2004, but not for the later years. There were 35, 63, 81 and 58 sites with P. ramorum in the semi-natural environment (SNE). Analyses were carried out to assess whether infected GCN sites could act as an inoculum source of infected SNE plants or vice versa. In all years, there was a significant spatial closeness among GCN and SNE outbreak sites within a distance of 1 km. But a significant relationship over a longer distance (within 60 km) was only observed between cases in 2003 and 2004. These analyses suggest that statutory actions taken so far appear to have reduced the extent of long-distance spread of P. ramorum among garden centres and nurseries, but not the disease spread at a shorter distance between GCN and SNE sites.

Gene flow, risk assessment and the environmental release of transgenic plants

The release of genetically modified plants is governed by regulations that aim to provide an assessment of potential impact on the environment. One of the most important components of this risk assessment is an evaluation of the probability of gene flow. In this review, we provide an overview of the current literature on gene flow from transgenic plants, providing a framework of issues for those considering the release of a transgenic plant into the environment. For some plants gene flow from transgenic crops is well documented, and this information is discussed in detail in this review. Mechanisms of gene flow vary from plant species to plant species and range from the possibility of asexual propagation, short- or long-distance pollen dispersal mediated by insects or wind and seed dispersal. Volunteer populations of transgenic plants may occur where seed is inadvertently spread during harvest or commercial distribution. If there are wild populations related to the transgenic crop then hybridization and eventually introgression in the wild may occur, as it has for herbicide resistant transgenic oilseed rape (Brassica napus). Tools to measure the amount of gene flow, experimental data measuring the distance of pollen dispersal, and experiments measuring hybridization and seed survivability are discussed in this review. The various methods that have been proposed to prevent gene flow from genetically modified plants are also described. The current "transgenic traits'! in the major crops confer resistance to herbicides and certain insects. Such traits could confer a selective advantage (an increase in fitness) in wild plant populations in some circumstances, were gene flow to occur. However, there is ample evidence that gene flow from crops to related wild species occurred before the development of transgenic crops and this should be taken into account in the risk assessment process.

Disease progression in heterosexual patients infected with closely related subtype B strains of HIV type 1 with differing coreceptor usage properties

Previously we described a heterosexual outbreak of HIV-1 subtype B in a town in the north of England (Doncaster) where 11 of 13 infections were shown to be linked by phylogenetic analysis of the env gp120 region. The 11 infections were related to a putative index case, Don1, and further divided into two groups based on the patients' disease status, their viral sequences, and other epidemiological information. Here we describe two further findings. First, we found that viral isolates and gp120 recombinant viruses derived from patients from one group used the CCR5 coreceptor, whereas viruses from the other group could use both the CCR5 and CXCR4 coreceptors. Patients with the X4/R5 dual tropic strains were symptomatic when diagnosed and progressed rapidly, in contrast to the other patient group that has remained asymptomatic, implying a link between the tropism of the strains and disease outcome. Second, we present additional sequence data derived from the index case, demonstrating the presence of sequences from both clades, with an average interclade distance of 9.56%, providing direct evidence of a genetic link between these two groups. This new study shows that Don1 harbored both strains, implying he was either dually infected or that over time intrahost diversification from the R5 to R5/X4 phenotype occurred. These events may account for/have led to the spread of two genetically related strains with different pathogenic properties within the same heterosexual community.

Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).