feos 0.9.5

FeOs - A framework for equations of state and classical density functional theory.
Documentation 
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use super::WeeksChandlerAndersen;
use super::hard_sphere::{
    dimensionless_diameter_q_wca, packing_fraction, packing_fraction_a_uvb3,
    packing_fraction_b_uvb3,
};
use crate::uvtheory::parameters::*;
use feos_core::StateHD;
use num_dual::DualNum;
use std::f64::consts::PI;

#[derive(Debug, Clone)]
pub(super) struct ReferencePerturbationB3;

impl ReferencePerturbationB3 {
    /// Helmholtz energy for perturbation reference (Mayer-f), eq. 29
    pub fn helmholtz_energy_density<D: DualNum<f64> + Copy>(
        &self,
        parameters: &UVTheoryPars,
        state: &StateHD<D>,
    ) -> D {
        let p = parameters;
        let n = p.sigma.len();
        let x = &state.molefracs;
        let d = WeeksChandlerAndersen::diameter_wca(p, state.temperature);
        //let q = diameter_q_wca(&p, state.temperature);
        let eta = packing_fraction(&state.partial_density, &d);
        let eta_a = packing_fraction_a_uvb3(p, eta, state.temperature);
        let eta_b = packing_fraction_b_uvb3(p, eta, state.temperature);
        let mut a = D::zero();

        for i in 0..n {
            for j in 0..n {
                let rs_ij = ((p.rep[i] / p.att[i]).powf(1.0 / (p.rep[i] - p.att[i]))
                    + (p.rep[j] / p.att[j]).powf(1.0 / (p.rep[j] - p.att[j])))
                    * 0.5; // MIXING RULE not clear!!!
                let d_ij = (d[i] + d[j]) * 0.5; // (d[i] * p.sigma[i] + d[j] * p.sigma[j]) * 0.5;

                let t_ij = state.temperature / p.eps_k_ij[(i, j)];
                let rep_ij = p.rep_ij[(i, j)];
                let att_ij = p.att_ij[(i, j)];
                let q_ij = dimensionless_diameter_q_wca(t_ij, D::from(rep_ij), D::from(att_ij))
                    * p.sigma_ij[(i, j)];

                a += x[i]
                    * x[j]
                    * ((-eta_a[(i, j)] * 0.5 + 1.0) / (-eta_a[(i, j)] + 1.0).powi(3)
                        * (-q_ij.powi(3) + (rs_ij * p.sigma_ij[(i, j)]).powi(3))
                        - ((-eta_b[(i, j)] * 0.5 + 1.0) / (-eta_b[(i, j)] + 1.0).powi(3))
                            * (-d_ij.powi(3) + (rs_ij * p.sigma_ij[(i, j)]).powi(3)))
            }
        }

        -a * state.partial_density.sum().powi(2) * 2.0 / 3.0 * PI
    }
}

#[cfg(test)]
mod test {
    use super::*;
    use crate::uvtheory::Perturbation::WeeksChandlerAndersenB3 as WCAB3;
    use crate::uvtheory::parameters::utils::test_parameters;
    use approx::assert_relative_eq;
    use nalgebra::dvector;

    #[test]
    fn test_delta_a0_uvb3_pure() {
        // #temp = 2.0, rho = 0.5, nu = 12
        // Hard sphere adhs  1.3491645849732654
        // Delta a0           0.1130778070897391

        let reduced_temperature = 2.0;
        let reduced_density = 0.5;

        let p = test_parameters(12.0, 6.0, 1.0, 1.0, WCAB3);
        let state = StateHD::new(reduced_temperature, 1.0 / reduced_density, &dvector![1.0]);
        let a = ReferencePerturbationB3.helmholtz_energy_density(&p, &state) / reduced_density;
        dbg!(a);
        assert_relative_eq!(a, 0.1130778070897391, epsilon = 1e-10);

        // #temp = 3.0, rho = 1.1, nu = 20
        // Hard sphere adhs  5.458989212531771
        //Delta a0  0.3405167374787895
        let reduced_temperature = 3.0;
        let reduced_density = 1.1;

        let p = test_parameters(20.0, 6.0, 1.0, 1.0, WCAB3);
        let state = StateHD::new(reduced_temperature, 1.0 / reduced_density, &dvector![1.0]);
        let a = ReferencePerturbationB3.helmholtz_energy_density(&p, &state) / reduced_density;

        assert_relative_eq!(a, 0.3405167374787895, epsilon = 1e-10);
    }
}