diff --git a/include/integratorxx/atomic_densities/SlaterAtomicShell.hpp b/include/integratorxx/atomic_densities/SlaterAtomicShell.hpp index 4d495c1..92a27f8 100644 --- a/include/integratorxx/atomic_densities/SlaterAtomicShell.hpp +++ b/include/integratorxx/atomic_densities/SlaterAtomicShell.hpp @@ -129,23 +129,27 @@ class SlaterTypeAtomicShell { } /// Helper to evaluate electron density gradient - double evaluate_tau(const double *dorbs, const int_container &occs) { + double evaluate_tau(double r, const double *orbs, const double *dorbs, + const int_container &occs) { double tau = 0.0; for(size_t iorb = 0; iorb < occs.size(); iorb++) { - tau += occs[iorb] * dorbs[iorb] * dorbs[iorb]; + tau += occs[iorb] * (dorbs[iorb] * dorbs[iorb] + + angular_momentum_ * (angular_momentum_ + 1) * + orbs[iorb] * orbs[iorb] / (r * r)); } tau *= 0.5; return tau; } /// Helper to evaluate electron density laplacian - double evaluate_density_laplacian(const double *orbs, const double *dorbs, - const double *lorbs, + double evaluate_density_laplacian(double r, const double *orbs, + const double *dorbs, const double *lorbs, const int_container &occs) { double lapl = 0.0; for(size_t iorb = 0; iorb < occs.size(); iorb++) { lapl += 2.0 * occs[iorb] * - (dorbs[iorb] * dorbs[iorb] + orbs[iorb] * lorbs[iorb]); + (dorbs[iorb] * dorbs[iorb] + orbs[iorb] * lorbs[iorb] + + 2.0 / r * orbs[iorb] * dorbs[iorb]); } return lapl; } @@ -173,27 +177,28 @@ class SlaterTypeAtomicShell { } /// Evaluates alpha electron density from computed orbitals - double evaluate_alpha_tau(const double *dorbs) { - return evaluate_tau(dorbs, alpha_occupations_); + double evaluate_alpha_tau(double r, const double *orbs, const double *dorbs) { + return evaluate_tau(r, orbs, dorbs, alpha_occupations_); } /// Evaluates beta electron density from computed orbitals - double evaluate_beta_tau(const double *dorbs) { - return evaluate_tau(dorbs, beta_occupations_); + double evaluate_beta_tau(double r, const double *orbs, const double *dorbs) { + return evaluate_tau(r, orbs, dorbs, beta_occupations_); } /// Evaluates alpha electron density from computed orbitals - double evaluate_alpha_density_laplacian(const double *orbs, + double evaluate_alpha_density_laplacian(double r, const double *orbs, const double *dorbs, const double *lorbs) { - return evaluate_density_laplacian(orbs, dorbs, lorbs, alpha_occupations_); + return evaluate_density_laplacian(r, orbs, dorbs, lorbs, + alpha_occupations_); } /// Evaluates beta electron density from computed orbitals - double evaluate_beta_density_laplacian(const double *orbs, + double evaluate_beta_density_laplacian(double r, const double *orbs, const double *dorbs, const double *lorbs) { - return evaluate_density_laplacian(orbs, dorbs, lorbs, beta_occupations_); + return evaluate_density_laplacian(r, orbs, dorbs, lorbs, beta_occupations_); } /// Return angular momentum @@ -333,9 +338,11 @@ class SlaterEvaluator { double evaluate_alpha_tau(double r) { double tau = 0.0; for(auto shell : atom_.shells()) { + shell.evaluate_basis_functions(r, bf_.data()); shell.evaluate_basis_function_gradients(r, df_.data()); + shell.evaluate_orbitals(bf_.data(), orbs_.data()); shell.evaluate_orbitals(df_.data(), dorbs_.data()); - tau += shell.evaluate_alpha_tau(dorbs_.data()); + tau += shell.evaluate_alpha_tau(r, orbs_.data(), dorbs_.data()); } return tau; } @@ -343,9 +350,11 @@ class SlaterEvaluator { double evaluate_beta_tau(double r) { double tau = 0.0; for(auto shell : atom_.shells()) { + shell.evaluate_basis_functions(r, bf_.data()); shell.evaluate_basis_function_gradients(r, df_.data()); + shell.evaluate_orbitals(bf_.data(), orbs_.data()); shell.evaluate_orbitals(df_.data(), dorbs_.data()); - tau += shell.evaluate_beta_tau(dorbs_.data()); + tau += shell.evaluate_beta_tau(r, orbs_.data(), dorbs_.data()); } return tau; } @@ -360,7 +369,7 @@ class SlaterEvaluator { shell.evaluate_orbitals(df_.data(), dorbs_.data()); shell.evaluate_orbitals(lf_.data(), lorbs_.data()); lapl += shell.evaluate_alpha_density_laplacian( - orbs_.data(), dorbs_.data(), lorbs_.data()); + r, orbs_.data(), dorbs_.data(), lorbs_.data()); } return lapl; } @@ -374,8 +383,8 @@ class SlaterEvaluator { shell.evaluate_orbitals(bf_.data(), orbs_.data()); shell.evaluate_orbitals(df_.data(), dorbs_.data()); shell.evaluate_orbitals(lf_.data(), lorbs_.data()); - lapl += shell.evaluate_beta_density_laplacian(orbs_.data(), dorbs_.data(), - lorbs_.data()); + lapl += shell.evaluate_beta_density_laplacian( + r, orbs_.data(), dorbs_.data(), lorbs_.data()); } return lapl; }