Differences in measures of the fiscal multiplier and the reduced-form vector autoregression
Summary (2 min read)
1. Introduction
- Since the first observations of photoconductivity in organic materials[1], the scientific interest in organic solar cells (OSCs) as important candidates for a reliable and economically viable renewable energy technology has increased enormously[2, 3, 4, 5].
- Given the relative energy level alignment of the three components (Fig. 1, right), it is required that the Si-PCPDTBT sensitizer is spatially separated from fullerene phase.
- In the light of these findings, as a first-step towards the modeling of complex ternary blends, it is of primary importance to study comparatively the binary interactions and miscibility of different polymers with fullerenes and to clarify the physical quantities (such as the concentration and density) that control the miscibility and the interfaces.
- PTB7-th and Si-PCPDTBT with the fullerenederivative PC71BM, by calculating the mixing free energy as a function of the relative polymer:fullerene concentration and blend density.the authors.
2. Results and discussion
- The authors calculate the free energy change ∆Gm/Vm upon mixing the polymers with the fullerene acceptor.
- In order to calculate ∆Hm/Vm, for each relative concentration, 10 starting configurations with different distribution of the fullerenes in the polymer matrix are considered, for a total of∼500 structures, and annealed at room temperature and pressure for ∼20 ns.
- Nevertheless, the local minima observed at specific concentrations (e.g. fullerene weight ratio of 50% for PTB7, 65% for PTB7-th and 68% for Si-PCPDTBT) allow to realize kinetically stable BHJs[14].
- The case of Si-PCPDTBT versus PTB7-th is less obvious since the corresponding ∆Hm/Vm curves intersect at several concentrations.
- In order to explain the dependence of ∆Hm/Vm on fullerene weight ratio (x) the authors consider a simple model based on the matching between the average fullerene-fullerene distance d and the polymer period L.
2.1. Effect of non-equilibrium conditions
- The results described in Fig. 2 are obtained in ideal conditions and at equilibrium density, but polymer blends are processed from solution using different solvents and deposition techniques.
- The density of the blend is rapidly increased as the solvent evaporates and, at given density, the blend morphology starts to form.
- Fullerene weight ratio, the enthalpy of mixing depends on the density of the blend, also known as At fixed polymer.
- This is an important result that shows the impact of density on the miscibility of the donor:acceptor pair and, in turn, on the final morphology of the blends obtained during nonequilibrium conditions occurring during layer processing.
- Nevertheless, their analysis at variable density gives useful indications at an affordable computational cost.
2.2. Microscopic analysis of the blends
- In order to provide physical (i.e. microscopic) insight into the values of ∆Hm/Vm reported in Figs. 2 and 4, the authors have separated the different contributions of ∆Hm/Vm (also indicated as potential energy, Ep).
- This can attributed to the stiffness of the polymer; when PTB7-th and fullerenes are closely-packed the π −π interactions are stronger (lowering dispersive energy) but the polymer chains undergo larger distortions (increasing the dihedral energy).
- This is confirmed also by the radial pair distribution functions g(r) (see Fig. S3 in SI) that indicates higher aggregation in PTB7-th.
- The results are reported in Table 1 and show that the highest adhesion to fullerenes is that of PTB7-th, followed by PTB7 and Si-PCPDTBT.
- The energy cost of bending (dihedral term) increases rapidly for the more rigid PTB7-th so that the rather flexible PTB7 polymer is energetically favored and has better miscibility with fullerenes.
3. Conclusions
- By using the Flory-Huggins theory, the authors have calculated through atomistic simulations the free energy of mixing of three polymer:fullerene blends as a function of their relative concentration and density.
- Since a hole transfer from the host to the sensitizer is expected, the predicted placement is able to deactivate hole traps and enhance the fill factor of the cell, as observed in experiments.
- The qualitative ∆Hm/Vm dependence on fullerene weight ratio is shown to be related to the matching between the average fullerene-fullerene distance and the polymer period.
- The detailed microscopic understanding of the miscibility requires to break down the enthalpy into different contributions.
- For PTB7-th blends the authors find a competition between the π−π polymer-fullerene interaction and polymer torsional energy, which is not found in PTB7 and Si-PCPDTBT.
Did you find this useful? Give us your feedback
Citations
4 citations
References
2,058 citations
"Differences in measures of the fisc..." refers background or methods in this paper
...Following the terminology in Uhlig (2005) and using Proposition A.1 therein, this vector can be obtained as a ¼ Cα where α is an N dimensional vector of unit length and C is the Cholesky decomposition of ∑....
[...]
...Also, sign restrictions (Uhlig 2005) based on a priori thoughts about the sign of the impact of fiscal policy can be considered....
[...]
...Because the Cholesky decomposition of ∑ is unique, if ∑P1 ≠ ∑P2, the corresponding Cholesky decompositions CP1 and CP2 satisfy CP1 CP2 (3) From Uhlig (2005), we know that α is given by R....
[...]
1,798 citations
1,737 citations
940 citations
600 citations
Related Papers (5)
Frequently Asked Questions (3)
Q2. What are the future works mentioned in the paper "Differences in measures of the fiscal multiplier and the reduced-form vector autoregression" ?
A formal derivation of a statistical test based on this idea is left for future work.
Q3. What is the proof of the theorem?
The theorem shows that, independently of identification assumptions, different reduced-form parameters induce (asymptotically and generically) different IRFs to a fiscal policy shock.