Vibrational Spectroscopy of Conducting Polymers: Theory and Perspective

Zerbi, G.

doi:10.1002/9780470027325.s8920

Cited by 22 publications

(45 citation statements)

References 111 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The normal mode eigenvectors show this mode to be predominantly expansion and contraction of the double and single bonds with opposite phase, in agreement with our understanding of the nature of the electronic excitation of polyenes [25]. This motion is thus along the Peierls' deformation coordinate [18,[23][24][25][26][27].…”

Section: Vibrations Of Polyacetylenesupporting

confidence: 72%

Bond alternation in infinite periodic polyacetylene: Dynamical treatment of the anharmonic potential

Hudson

Allis

2013

Journal of Molecular Structure

View full text Add to dashboard Cite

Section: Vibrations Of Polyacetylenesupporting

confidence: 72%

Bond alternation in infinite periodic polyacetylene: Dynamical treatment of the anharmonic potential

Hudson

Allis

2013

Journal of Molecular Structure

View full text Add to dashboard Cite

“…We now turn to Raman spectroscopy to obtain a deeper insight into the neutron-induced modifications of the two polymer films since Raman and more generally vibrational spectroscopies have been used effectively to assess fundamental structure-property relationships of polyconjugated systems2829.…”

Section: Resultsmentioning

confidence: 99%

Neutron Radiation Tolerance of Two Benchmark Thiophene-Based Conjugated Polymers: the Importance of Crystallinity for Organic Avionics

Paternò

Robbiano

Fraser

et al. 2017

Sci Rep

View full text Add to dashboard Cite

Aviation and space applications can benefit significantly from lightweight organic electronics, now spanning from displays to logics, because of the vital importance of minimising payload (size and mass). It is thus crucial to assess the damage caused to such materials by cosmic rays and neutrons, which pose a variety of hazards through atomic displacements following neutron-nucleus collisions. Here we report the first study of the neutron radiation tolerance of two poly(thiophene)s-based organic semiconductors: poly(3-hexylthiophene-2,5-diyl), P3HT, and the liquid-crystalline poly(2,5-bis (3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene), PBTTT. We combine spectroscopic investigations with characterisation of intrinsic charge mobility to show that PBTTT exhibits significantly higher tolerance than P3HT. We explain this in terms of a superior chemical, structural and conformational stability of PBTTT, which can be ascribed to its higher crystallinity, in turn induced by a combination of molecular design features. Our approach can be used to develop design strategies for better neutron radiation-tolerant materials, thus paving the way for organic semiconductors to enter avionics and space applications.

show abstract

“…In the literature, the effective conjugation coordinate (ECC) theory has been already widely used for the interpretation, in molecular terms, of the Raman spectra of polyconjugated chains mainly focused at the confinement of π electrons …”

Section: Introductionmentioning

confidence: 99%

“…In this paper, we proceed to the interpretation of the Raman spectra of carotenoid molecules in terms of the ECC theory …”

Section: Introductionmentioning

confidence: 99%

Raman spectroscopy of polyconjugated molecules with electronic and mechanical confinement: the spectrum of Corallium rubrum

Tommasini

Zerbi

Stradi

2012

J Raman Spectroscopy

Self Cite

View full text Add to dashboard Cite

The chemical nature of the red pigment of Corallium rubrum (CR) has not yet been clearly identified. We have recorded the Raman spectra of CR, canthaxantin, and parrot feather, and we propose an interpretation with the help of quantum chemistry and of the effective conjugation coordinate theory, which accounts for the main Raman lines (n 1 , n 2 , n 3 ) as originating from the polyene backbone. In this study, two additional lines in the 1000 cm À1 range (n 4 and n 5 ) are considered as well as a series of overtones and combinations in the second order Raman spectrum (2000-3000 cm À1 ). Density Functional Theory calculations predict that, moving with successive methylation from a simple unsubstituted polyene chain with 9 C¼C bonds (as psyttacofulvins) to a 9, 9′, 13, 13′ tetramethylated chain (as carotenoids), the geometric structures of the molecules and their Raman spectra show changes that can be rationalized if the effective conjugation coordinate theory is extended to account for mechanical confinement. This turns out to be a new concept that helps the interpretation of the Raman spectra of partially methylated conjugated oligoenes. Evidence is found that the main component of the pigment of CR does not posess a fully demethylated polyene chain (psyttacofulfine) nor a tetramethylated chain (carotenoid), thus indicating that the polyene chain is partially methylated. Because we consider resonance Raman spectra, the target of this study is the structure of the polyene backbone; no direct spectroscopic information can be obtained in this way on the chemical nature of the groups attached to both chain ends. Figure 2. (a) Simplified molecular model of a linear polyene chain with the numbering of the unit cells and the definition of the internal vibrational displacement coordinates R (C¼C stretch) and r (CÀC stretch) according to Wilson; [28] (b) sketch of the collective Я coordinate defined by Eqn. (3).Raman spectroscopy of polyconjugated molecules with electronic and mechanical confinement

show abstract

Vibrational Spectroscopy of Conducting Polymers: Theory and Perspective

Abstract: The sections in this article are Introduction Why New Science and Innovative Technology with Polyconjugated Systems? The World of π Electrons The Theoretical Approach to Molecular Vibrations of Polyconjugated Molecules Electron Phonon Coupling AB Initio Calculations … Show more

Cited by 22 publications

References 111 publications

Bond alternation in infinite periodic polyacetylene: Dynamical treatment of the anharmonic potential

Bond alternation in infinite periodic polyacetylene: Dynamical treatment of the anharmonic potential

Neutron Radiation Tolerance of Two Benchmark Thiophene-Based Conjugated Polymers: the Importance of Crystallinity for Organic Avionics

Raman spectroscopy of polyconjugated molecules with electronic and mechanical confinement: the spectrum of Corallium rubrum

Contact Info

Product

Resources

About