1. Introduction

1.1. Parameter Fitting: A Lennard-Jones Example

Assuming we are interested in calculating the potential energy \({V}(R)\) between two Argon atoms, one suitable model for this task is the Lennard-Jones Potential (LJ), which is given by

(1.1)\[\hat{V}(R|\mathrm{\boldsymbol{x}}) = \frac{{x_1}}{R^{12}} - \frac{{x_2}}{R^6},\]

where \(\hat{V}\) is the (predicted) potential energy as a function of the interatomic distance \(R\) and a parameter vector \(\boldsymbol{x}=({x_ 1}, {x_2})^\mathrm{T}\) that modifies the shape of the potential.

If reference data \(\boldsymbol{y} = \{(R_i,V_i)\}\) is available for this problem (either from an experiment or another model), we can measure the quality of the LJ model by a loss function (also called objective or cost function) \(L\), which is a metric operating on the residuals vector \(\boldsymbol{y} - \boldsymbol{\hat{y}} = \{V_i - \hat{V}_i\}\). One example for such a metric is the mean absolute error (MAE):

(1.2)\[L_\mathrm{MAE}( \boldsymbol{y} - \boldsymbol{\hat{y}} ) = \frac{1}{N} \sum_{i=1}^N | y_i - \hat{y}_i |.\]

For a case when the LJ model perfectly represents the experimental data, \(\boldsymbol{y} = \boldsymbol{\hat{y}}\), and \(L=0\). In contrast, a larger loss function value represents a mismatch between the predicted and reference values. In such cases the parametric model’s parameters can be fitted, assuming the reference set of systems and energies does not change during the optimization process. We introduce an optimizer which produces an optimized set of parameters \(\boldsymbol{x}^*\) from an initial point \(\boldsymbol{x}_0\) by minimizing \(L\):

(1.3)\[O(\boldsymbol{x}_0, L) = \underset{\boldsymbol{x}} {\mathop{\mathrm{arg\,min}}}\, L = \boldsymbol{x}^*.\]

We visualize the influence of two different parameter sets for the Lennard-Jones potential in the figure below: While the initial model parameters (orange curve) might not represent experimental data (discrete marks) very well, an optimization of the parameters with respect to the reference data can provide a viable solution (grey curve).


1.2. General Application

In a more generalized description of the package, ParAMS allows its users to fit a variety of parametric (empirical) models that are part of the Amsterdam Modeling Suite. By design, any physico-chemical property \(P\) that can be extracted from one AMS computation (or constructed from multiple), can be fitted with a number of different optimization algorithms. A minimal set up does not require much more additional user input, making setting up of basic workflows easy and accessible.

At the same time ParAMS offers a variety of additional features for the customization of the workflow such as automated and manual definition of the search space and relevant parameter subsets, support for validation sets or additional interaction through callbacks to name a few, resulting in a package that is highly flexible when it comes to advanced user requirements.

Integration with AMS guarantees that the same APIs are supported regardless of the application, making workflows highly reusable and storage of relevant reference data in the human-readable YAML format ensures transparency and reproducibility.