Ten novel fullerene-derivatives (FDs) of C60 and C70 had been designed as acceptor for polymer solar cell (PSC) by employing the quantitative structure-property relationship (QSPR) model, which was developed strategically with a reasonably big pool of experimental power conversion efficiency (PCE) data. The QSPR model was checked and validated with stringent parameter and reliability of predicted PCE values of all designed FDs. They were assessed by the applicability domain (AD) and process randomization test. The predicted PCE of FDs range from 7.96 to 23.01. The obtained encouraging results led us to the additional theoretical analysis of the energetics and UV-Vis spectra of isolated dyes employing Density functional theory (DFT) and Time-dependent-DFT (TD-DFT) calculations using PBE/6-31G(d,p) and CAM-B3LYP/6-311G(d,p) level calculations, respectively. The FD4 is the best C60-derivatives candidates for PSCs as it has the lowest exciton binding energy, up-shifted lowest unoccupied molecular orbital (LUMO) energy level to increase open-circuit voltage (VOC) and strong absorption in the UV region. In case of C70-derivatives, FD7 is potential candidate for future PSCs due to its strong absorption in UV-Vis region and lower exciton binding energy with higher VOC. Our optoelectronic results strongly support the developed QSPR model equation. Analyzing QSPR model and optoelectronic parameters, we concluded that the FD1, FD2, FD4, and FD10 are the most potential candidates for acceptor fragment of fullerene-based PSC. The outcomes of tactical molecular design followed by the investigation of optoelectronic features are suggested to be employed as a significant resource for the synthesis of FDs as an acceptor of PSCs.
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Evaluation of the degree of rate control via automatic differentiation
The degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate‐limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady‐state and transient kinetics. Furthermore, we illustrate a hybrid local‐global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high‐quality results efficiently.
more » « less- Award ID(s):
- 1921946
- NSF-PAR ID:
- 10370100
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- AIChE Journal
- Volume:
- 68
- Issue:
- 6
- ISSN:
- 0001-1541
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Algorithmic differentiation (AD), also known as automatic differentiation, is a technology for accurate and efficient evaluation of derivatives of a function given as a computer model. The evaluations of such models are essential building blocks in numerous scientific computing and data analysis applications, including optimization, parameter identification, sensitivity analysis, uncertainty quantification, nonlinear equation solving, and integration of differential equations. We provide an introduction to AD and present its basic ideas and techniques, some of its most important results, the implementation paradigms it relies on, the connection it has to other domains including machine learning and parallel computing, and a few of the major open problems in the area. Topics we discuss include: forward mode and reverse mode of AD, higher‐order derivatives, operator overloading and source transformation, sparsity exploitation, checkpointing, cross‐country mode, and differentiating iterative processes.
This article is categorized under:
Algorithmic Development > Scalable Statistical Methods
Technologies > Data Preprocessing
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An improved version of the Fast automatic Differentiation using Operator-overloading Technique (FDOT) toolbox is developed in this work. The enhanced sensitivity analysis toolbox utilizes an expression-based tape approach -- a first-of-its-kind implementation in Fortran programming language -- that can significantly reduce the memory footprint while improving the computational efficiency of the adjoint-based automatic differentiation (AD). In the proposed approach, the partial derivatives are calculated for each expression using the reverse adjoint accumulation for the active variables involved on the right-hand-side of that expression. The recorded partial derivative information is then used in a very efficient adjoint evaluation process to calculate the entire Jacobian information. The enhanced toolbox is coupled with the in-house UNstructured PArallel Compressible (UNPAC) flow solver for a robust design optimization framework, called UNPAC-DOF. The efficiency and robustness of the proposed technique and the resulting framework are tested for aerodynamic shape optimization problems applied to airfoil and wing geometries.more » « less
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Jones, Chris (Ed.)In this paper, we discuss the concept and properties of variance-based global sensitivity analysis, as an expansion of local sensitivity metrics (such as the degree of rate control), for modeling and design of catalytic reaction systems. Using an illustrative example and supporting theory, we show that: (i) for small variations in the parameters, global sensitivities are similar to local derivatives; (ii) for larger variations in the parameters (i.e., a larger parameter space), the global sensitivities provide a ranking of importance of parameters and impose a rigorous bound on the errors that arise from fixing one or more parameters to nominal values; and (iii) in general, the global sensitivities can be related to the extrema of local derivatives. We argue that the square root of the total global sensitivity of a parameter, computed by summing the global sensitivity of that parameter acting independently and in combination with others, is a “global” degree of rate control for catalytic systems.more » « less
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SUMMARY A key initial step in geophysical imaging is to devise an effective means of mapping the sensitivity of an observation to the model parameters, that is to compute its Fréchet derivatives or sensitivity kernel. In the absence of any simplifying assumptions and when faced with a large number of free parameters, the adjoint method can be an effective and efficient approach to calculating Fréchet derivatives and requires just two numerical simulations. In the Glacial Isostatic Adjustment problem, these consist of a forward simulation driven by changes in ice mass and an adjoint simulation driven by fictitious loads that are applied at the observation sites. The theoretical basis for this approach has seen considerable development over the last decade. Here, we present the final elements needed to image 3-D mantle viscosity using a dataset of palaeo sea-level observations. Developments include the calculation of viscosity Fréchet derivatives (i.e. sensitivity kernels) for relative sea-level observations, a modification to the numerical implementation of the forward and adjoint problem that permits application to 3-D viscosity structure, and a recalibration of initial sea level that ensures the forward simulation honours present-day topography. In the process of addressing these items, we build intuition concerning how absolute sea-level and relative sea-level observations sense Earth’s viscosity structure and the physical processes involved. We discuss examples for potential observations located in the near field (Andenes, Norway), far field (Seychelles), and edge of the forebulge of the Laurentide ice sheet (Barbados). Examination of these kernels: (1) reveals why 1-D estimates of mantle viscosity from far-field relative sea-level observations can be biased; (2) hints at why an appropriate differential relative sea-level observation can provide a better constraint on local mantle viscosity and (3) demonstrates that sea-level observations have non-negligible 3-D sensitivity to deep mantle viscosity structure, which is counter to the intuition gained from 1-D radial viscosity Fréchet derivatives. Finally, we explore the influence of lateral variations in viscosity on relative sea-level observations in the Amundsen Sea Embayment and at Barbados. These predictions are based on a new global 3-D viscosity inference derived from the shear-wave speeds of GLAD-M25 and an inverse calibration scheme that ensures compatibility with certain fundamental geophysical observations. Use of the 3-D viscosity inference leads to: (1) generally greater complexity within the kernel; (2) an increase in sensitivity and presence of shorter length-scale features within lower viscosity regions; (3) a zeroing out of the sensitivity kernel within high-viscosity regions where elastic deformation dominates and (4) shifting of sensitivity at a given depth towards distal regions of weaker viscosity. The tools and intuition built here provide the necessary framework to explore inversions for 3-D mantle viscosity based on palaeo sea-level data.
