Valence Transfer Research Articles

Election Poster Persuasion

Abstract. We examined the effect of presenting unknown policy statements on German parties’ election posters. Study 1 showed that participants inferred the quality of a presented policy from knowledge about the respective political party. Study 2 showed that participants’ own political preferences influenced valence estimates: policy statements presented on campaign posters of liked political parties were rated significantly more positive than those presented on posters of disliked political parties. Study 3 replicated the findings of Study 2 with an additional measure of participants’ need for cognition. Need for cognition scores were unrelated to the valence transfer from political parties to policy evaluation. Study 4 replicated the findings of Studies 2 and 3 with an additional measure of participants’ voting intentions. Voting intentions were a significant predictor for valence transfer. Participants credited both their individually liked and disliked political parties for supporting the two unknown policies. However, the credit attributed to the liked party was significantly higher than to the disliked one. Study 5 replicated the findings of Studies 2, 3, and 4. Additionally, participants evaluated political clubs that were associated with the same policies previously presented on election posters. Here, a second-degree transfer emerged: from party valence to policy evaluation and from policy evaluation to club evaluation. Implications of the presented studies for policy communications and election campaigning are discussed.

Valence transfer of Eu3+ activated in Yb2Si2O7 phosphors: Luminescence and self reduction

Generally, the reduction of Eu3+ to Eu2+ in solids requires annealing in a reducing atmosphere. In this work, we find that the reduction of Eu3+ to Eu2+ can be realized in Yb2Si2O7 phosphors after being soaked in boiling water. Eu3+-activated Yb2Si2O7 with different doping concentrations was synthesized by a sol-gel method. The as-prepared Yb2Si2O7:Eu3+ phosphors showed strong red emission at 612 nm under ultraviolet light, corresponding to the 5D0 → 7F2 transition of Eu3+. The optimized doping concentration of Eu3+ was 7 mol% with the highest emission intensity at 612 nm. The valence change and luminescence properties of Eu-doped Yb2Si2O7 phosphors after being soaked in boiling water are reported and the reduction mechanism from Eu3+ to Eu2+ in the compounds is discussed. Our findings suggest that this kind of Eu3+ → Eu2+ valence transfer might shed light on the development of phosphors for display applications.

A valence bond theory treatment of tetrel bonding interactions

Long range noncovalent interactions in H3Y…TrH3X molecules (Y=N, P, As; Tr=C, Si, Ge; X=F, Cl, Br) have been studied using valence bond methods in order to further the understanding of tetrel (group IV) bonding. It is shown that incorporating electron correlation through the breathing orbital valence bond method is required in order to reproduce tetrel bond energy trends obtained by density functional theory. Tetrel bonds are formed by donation of the Y lone pair into a σ-hole on the Tr atom and their strength depends on the donor strength of the Y atom and the Tr/X electronegativity difference. Charge transfer valence bond structures are shown to be important, indicating that electron transfer is the driving force behind tetrel bonds rather than electrostatics.

Electron densities over Si and O atoms of tetrahedra and their impact on Raman stretching frequencies and Si-NBO force constants

Systematics of SiO Raman stretching frequencies in the range 800–1200cm−1, and Si 2p and O 1s XPS binding energies (BE) are examined for a large number of alkali and alkaline earth silicate glasses, melts, and crystals. Several relationships in the Raman and X-ray Photoelectron spectral (XPS) data lead to new insights concerning charge delocalization over Si tetrahedra and to recognition of controls on both Raman stretching frequencies, and Si 2p and O 1s XPS chemical shifts. The Raman stretching frequencies of the five Q species and the Si 2p and O 1s XPS chemical shifts, vary linearly with the alkali and alkaline-earth content of glasses over the range 0–50mol% counter oxide (M2O or MO). The relationships demonstrate that the frequencies and chemical shifts are controlled by the same property, the valence band electron densities on the atoms of silicate tetrahedra. Specifically, where M-O ion interactions are strongly ionic, the number of NBO's attached to the central Si atom most affects the electron density of Si and O in tetrahedra, and is the major control on Raman symmetric stretching frequencies. Also, the Raman stretching frequency of individual Q species are effectively independent of the mass of the alkali counter cation (MNa, K, Rb, Cs).Addition of alkali oxides to vitreous SiO2 produces Si 2p and O 1s XPS chemical shifts. The magnitude of the chemical shifts increase with counter oxide abundance through transfer of valence ‘s’ electrons from alkali atoms to NBO of tetrahedra. The negative charge acquired by the NBO is redistributed (delocalized) over all atoms of the tetrahedron via SiO bonds thereby increasing valence band electron densities over the constituent Si and O atoms. The greater the number of NBOs associated with a tetrahedron the greater the enhancement of electron density on all atoms of the tetrahedron, thus explaining the Si 2p and O 1s XPS chemical shifts. With respect to Raman spectra, the increased valence electron density causes the central Si atom to become appreciably less positive, which diminishes the strength of Coulombic interactions between Si and O atoms, and weakens SiO force constants. In turn, the weakened force constants result in decreases to SiO stretching frequencies. The weakening of force constants and decrease in stretching frequencies occur in a stepwise manner and relate directly to the number of NBO attached to the tetrahedra. The SiO force constant for the Q4 species is much larger than the force constant for the Q0 species, causing their stretching frequencies to decrease (stepwise) from ~1200cm−1 to ~850cm−1. The mathematical relationships among alkali oxide compositions, Raman stretching frequencies and XPS chemical shifts are quantified.

Doing is for feeling.

In 2 experiments we show that preferences can be formed by transfer of valence from an unconditioned stimulus (US) to an action and then from this valence-laden action to a novel conditioned stimulus (CS) even though the US and CS were never presented together. This result expands the approach of intersecting regularities (Hughes, De Houwer, & Perugini, 2016) to yet another realm of evaluative learning. In addition, our approach to evaluative learning suggests theoretical links between the formation of preferences due to actions and general research on action control. In summary, we discovered an additional route via which humans may acquire novel preferences and we propose a mental mechanism that may play an important role in the perceptuomotor system that controls many daily life behaviors. (PsycINFO Database Record

Automaticity and affective responses in valence transfer: Insights from the crossmodal auditory-visual paradigm

The current study examined valence transfer in the crossmodal paradigm in order to test the generalizability of the phenomenon and to contribute to a better understanding of the underlying processes. Western European participants evaluated Asian ideographs to be more visually pleasant when in the presence of pleasant sounds than when in the presence of neutral or unpleasant sounds (Experiment 1). Experiment 2 was conducted to reduce the demand characteristics, and to investigate the involvement of affective responses. We measured facial electromyography (EMG) and skin conductance responses (SCR) from participants evaluating ideographs while a piece of music was playing in the background. Evaluative judgments of the ideographs reflected subtle variance of valence within the piece of music. The extent of this valence transfer depended on the extent of SCRs within the respective trial. In addition, ideograph judgments were accompanied by concordant affective responses within facial EMG. The findings suggest that valence transfer from brief stimuli can be generalized to the crossmodal paradigm, occurs even if the experimental procedure obscures the purpose of investigation (i.e., automatically), and that affective responses are involved.

DNA damage by the sulfate radical anion: hydrogen abstraction from the sugar moiety versus one-electron oxidation of guanine

ABSTRACTThe products of oxidative damage to double-stranded (ds) DNA initiated by photolytically generated sulfate radical anions SO4•− were analyzed using reverse-phase (RP) high-performance liquid chromatography (HPLC). Relative efficiencies of two major pathways were compared: production of 8-oxoguanine (8oxoG) and hydrogen abstraction from the DNA 2-deoxyribose moiety (dR) at C1,′ C4,′ and C5′ positions. The formation of 8oxoG was found to account for 87% of all quantified lesions at low illumination doses. The concentration of 8oxoG quickly reaches a steady state at about one 8oxoG per 100 base pairs due to further oxidation of its products. It was found that another guanine oxidation product identified as 2-amino-5-(2′-alkylamino)-4H-imidazol-4-one (X) was released in significant quantities from its tentative precursor 2-amino-5-[(2′-deoxy-β-d-erythro-pentofuranosyl)amino]-4H-imidazol-4-one (dIz) upon treatment with primary amines in neutral solutions. The linear dose dependence of X release points to the formation of dIz directly from guanine and not through oxidation of 8oxoG. The damage to dR was found to account for about 13% of the total damage, with majority of lesions (33%) originating from the C4′ oxidation. The contribution of C1′ oxidation also turned out to be significant (17% of all dR damages) despite of the steric problems associated with the abstraction of the C1′-hydrogen. However, no evidence of base-to-sugar free valence transfer as a possible alternative to direct hydrogen abstraction at C1′ was found.

Expertise in video game playing is associated with reduced valence-concordant emotional expressivity.

In carefully selected groups of video game playing (VGP) experts and nonexperts, we examined valence-concordant emotional expressivity. We measured electromyographic (EMG) activity over the corrugator supercilii muscle while participants viewed pleasant, neutral, and unpleasant pictures. Potential group differences concerning valence-concordant expressivity may arise from differences concerning the participants' emotional reactivity. To control for such differences, we concomitantly measured skin conductance response (SCR) and, in a separate affect misattribution procedure (AMP), valence transfer from the same set of stimuli. Importantly, we found attenuated valence-concordant EMG activity over the corrugator supercilii muscle in VGP experts compared to nonexperts, but no differences were evident concerning SCR or valence transfer in the AMP. The findings suggest that expertise in VGP is particularly associated with reduced valence-concordant emotional expressivity.

Two in one conditioning? The role of valence in concept learning

The present two studies investigated whether semantic as well as evaluative stimulus aspects can be conditioned to neutral stimuli. In Study 1, pictures of large and small objects were paired with neutral stimuli (conditioned stimuli (CSs)). The subsequently assessed size and likeability ratings indicated that valence as well as size was transferred to the CSs. CSs paired with pictures showing large objects were judged as larger and more positive compared to CSs paired with pictures of small objects. Interestingly, however, concept conditioning did not depend on valence transfer, whereas the EC effect was driven by concept conditioning. This pattern was replicated in a second study in which the concept of softness was used as the to-be-conditioned concept.

Metaphor and Persuasive Communication: A Multifunctional Approach

Metaphors are pervasive in both mass communication and interpersonal exchanges and can play an important role in persuasion. Metaphor serves multiple functions in persuasive communication, and the effect of metaphor on persuasion is potentially mediated by multiple psychological process mechanisms. Nevertheless, we propose that past and future research in this area can be organized or grouped into three simple categories. First, metaphorical statements can activate information that is directly applied to the communication topic and thereby influence attitudes toward the communication topic. Second, metaphorical language may influence impressions of the communication source and thereby impact attitudes toward the communication topic. Third, metaphors may affect attitudes toward the communication topic by influencing the direction or amount of elaboration that takes place when recipients process literal statements contained in the communication. A review of past research is organized into these three categories, and proposals for future research in each category are introduced. It is concluded that future research within each of these domains should focus on two related questions: under what conditions does metaphor elicit a given psychological process in the receiver (e.g., attribute mapping, valence transfer), and under what conditions will a given process result in an increase versus decrease in persuasion?

When linking is stronger than thinking: Associative transfer of valence disrupts the emergence of cognitive balance after attitude change

The present research investigated the role of cognitive balance vs. associative transfer of valence in attitude change. Participants first formed positive or negative attitudes toward several source individuals. Subsequently, participants were shown source–target pairs along with information about the source–target relationship (‘likes’/‘dislikes’). Afterwards, participants’ attitudes toward the sources were changed by means of information that was opposite to the initially induced attitude. In a control condition, initial source attitudes remained unqualified. Results in the control condition showed that initially formed attitudes and available relationship information produced target evaluations that were consistent with the notion of cognitive balance. However, when attitudes toward the sources changed, target evaluations directly matched attitudes toward individually associated sources, irrespective of the relation between source and target. These results suggest that associative transfer of valence can disrupt the emergence of cognitive balance after attitude change.

Thermal study of monovalent-divalent phase transition in npBifc-F1TCNQ System

In a new molecular solid composed of di-neopentyl-biferrocene (npBifc) and fluorotetracyanoquinodimethane (F1TCNQ)3, Mochida reported the discovery of a reversible valence transfer that can be regarded as an "ionic(I)-ionic(II)" phase transfer between the monovalent state (D+A-) and the divalent state (D2+A2-). We have studied thermo-dynamical properties of this transformation for this complex using the differential thermal analyses (DTA). We observed a broad excess specific heat with multi-peaks attributed to micro-domain structure over the corresponding temperature range (100–150K) accompanied by temperature hysteresis of 7K. The transition entropy (ΔS) was determined to be 22 ± 2 J/mol-K and almost satisfied a Clausius-Clapeyron relation. These experimental results provide an experimental confirmation of the first order phase transition for the monovalent-divalent transfer. At the transition, we observe that the electronic degrees of freedom remained constant values, while large entropy absorbed crossing from low temperature phase to high temperature one is contributed by the lattice one. We finally estimated the internal energy and concluded that delicate energy valance between Madelung, ionization and affinity energies enable this system to exhibit a temperature induce monovalent-divalent phase transition.

Study on charge transfer interaction and valence state of layered perovskite-type mixed valence complex [NH3(CH2) n NH3]2[(AuII2)(AuIIII4)(I3)2] (n = 7, 8), by means of 197Au Mössbauer spectroscopy

Cs2[AuI X 2][AuIII X 4](X = Cl, Br, and I) is well known for the three-dimensional perovskite-type gold mixed valence system. Recently, layered perovskite-type gold mixed valence complexes, [NH3(CH2)nNH3]2[(AuII2)(AuIIII4)(I3)2] (n = 7 and 8), have been synthesized. We have investigated the relationship between the structural dimensionality and the AuI-AuIII charge transfer interaction for Cs2[AuII2][AuIIII4] and [NH3(CH2)nNH3]2[(AuII2)(AuIIII4)(I3)2] (n = 7 and 8) by means of 197Au Mossbauer spectroscopy.

Photoelectron spectra and surface valence fluctuation of Eu in the misfit-layer compound {(EuS) 1.15} 1.5NbS 2

The 1.5Q/1 H type of the misfit layer compound {(EuS) 1.15} 1.5NbS 2 has been studied by X-ray photoelectron spectroscopy. Eu 3d, 4d, 4f and 5p spectra are measured with Al and MgKα radiation. Their intensities are analyzed, taking the escape depth of photoelectrons emitted from the core levels into account. The results indicate that valence transfer of nearly-half Eu 2+ ions to Eu 3+ happens in the outermost surface layer and a reduced Eu–S distance brings about surface rearrangement. It is confirmed that Eu 2+ and Eu 3+ coexist in a bulk, in consistency with bond valence calculations and Mössbauer spectra. The XPS spectra are well interpreted in terms of the multiplet structures of Eu 2+ and Eu 3+.

Chain and monomolecular decomposition of hexogen in solutions

The decomposition of hexogen dissolved in alkylaromatic hydrocarbons, alcohols, ketones, ethers, chloroform, and some other solvents occurs via the chain mechanism. This mechanism is supported by slowing down of the reaction when inhibitors are added, the solvent deuterium kinetic isotope effect, and the dependence of the rate on the reactivity of the C—H bond in solvents. The chain reaction propagates through the transfer of a free valence from the primary N-radicals formed by N—NO2 bond dissociation to the C-centered radicals of the solvent. The solvents are inert when the N—H bond dissociation energy is >380 or <200 kJ mol–1, and hexogen decomposition in such solvents is monomolecular.

Superoxide dismutase inhibits lipid peroxidation in micelles

Superoxide dismutase (SOD) taken in minor concentrations (a few U/ml) displays a pronounced inhibiting effect on the chain oxidation of methyl linoleate and methyl linolenate (but not methyl oleate) induced by 2,2′-azobis(2-amidinopropan) dihydrochloride (AAPH) in micellar solutions of sodium dodecyl sulfate and Triton X-100 in phosphate buffer, pH 7.40, at 37.0°C. The inhibition is evidently caused by purging the system from O 2 −. The latter suggests the formation of O 2 − (HO 2 ) in the course of peroxidation, most likely, via β-decay of lipid peroxy radical (LO 2 ). Thermodynamic estimations verify a rather high probability of β-decay of LO 2 produced from polyunsaturated fatty acids by contrast to that produced from saturated and monoenic fatty acids. It is speculated that O 2 − (HO 2 ), being an amphiphilic, reactive and highly mobile species, participates in intermicellar (interliposomal) transfer of free valence during lipid peroxidation in microheterogeneous systems.

Enthalpies of elementary chain propagation steps in the oxidation of organic compounds

A calculation of the enthalpies of elementary steps of the intra- and intermolecular chain propagation for model oxidation reactions of ethers, esters, ketones and hydrocarbons has been carried out. The heats of the intermolecular and intramolecular transfer of free valence with participation of peroxy radicals and C−H bond of the oxygen-containing compounds are shown to be comparable.

Growth of Anodic films on valve metals

By analysis of transport number and F—log j data for valve metals under galvanostatic anodization, obedience is found to the kink dependent Cabrera—Mott equation for irreversible transfer of metal ions from metal to oxide and to the defect dependent high-field ion migration equation for transport of both metal and oxygen ions in the growing anodic film. For Al, the kink and defect dependences are d log s/d log j = 0.5 and d log N/d log j approaching 0.67 at low current densities (oxygen ion transport) and 0.5 at high ones (metal ion transport), and the ion transfer valence is n = 3. The denser is the oxygen packing in the oxide, the higher is the electric field needed to drive a given ionic current through it.

Anodic growth of passive films on tin

The title subject is studied by galvanostatic E—t curves on 20 h stabilized passive tin electrodes in weakly alkaline phosphate solution (pH 9.5) at 25°C. These curves generally exhibit a small initial superpolarization ascribed to transient changes in the surface density of kinks ( s) by the current density ( j) applied. Obedience is found to the Cabrera—Mott equation for irreversible metal ion transfer from kink sites in the metal surface and to the oxide film. For the steady-growth kink density and the ion transfer valence, it is found that d log s/d log j = 0.5 and n = 2, respectively. No space-charge effect is seen in passive films growing at rates up to 100 μA cm −2 (the highest current applied).

Environmental variables and releasing-valence transfer in stimulus-directed pecking of chicks

Releasing valence transfer occurs when the power or valence to release responses is transferred from a primary releasing stimulus to a second, initially neutral, stimulus. In the exemplar, pecking responses by neonatal chicks are released and directed by a pointed object operated to make pecking movements. Stimuli attached to or pecked by the arrow thereby acquire enhanced releasing valence. Chicks peck at matching stimuli in preference to comparable but unenhanced stimuli. Research reported here shows that primary and transferred releasing valences are differentially affected by environmental variables. Specific findings were Pecking by chicks occurs only within a narrow range of ambient temperature. Outside of this range, pecking is low in frequency and insensitive to valence-enhanced release. Pecking by chicks appears to be finely tuned to arrow peck rates between 120 and 180 pecks per minute. Within this range, frequency of pecks by chicks is low whereas the percentage of pecks to the valence-enhanced stimulus is maximal. The maternal food call was a weak releaser of pecking by chicks with no valence-enhancing properties.