Analytic Alchemical Derivatives for the Analysis of Differential Acidity Assisted by the <i>h</i> Function

Flores‐Moreno, Roberto; Cortés-Llamas, Sara A.; Pineda‐Urbina, Kayim; Medel, Victor M.; Jayaprakash, Gururaj Kudur

doi:10.1021/acs.jpca.1c07364

Cited by 7 publications

(4 citation statements)

References 74 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Finally, it is worth mentioning that ADFT enables the accurate calculation of energy derivatives of arbitrary order. − However, the current ADFT implementation in NWChem only supports the calculation of analytic nuclear gradients.…”

Section: Improvement To Existing Methods In Nwchemmentioning

confidence: 99%

NWChem: Recent and Ongoing Developments

Mejı́a-Rodrı́guez

Aprà

Autschbach

et al. 2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

This paper summarizes developments in the NWChem computational chemistry suite since the last major release (NWChem 7.0.0). Specifically, we focus on functionality, along with input blocks, that is accessible in the current stable release (NWChem 7.2.0) and in the "master" development branch, interfaces to quantum computing simulators, interfaces to external libraries, the NWChem github repository, and containerization of NWChem executable images. Some ongoing developments that will be available in the near future are also discussed.

show abstract

Section: Improvement To Existing Methods In Nwchemmentioning

confidence: 99%

NWChem: Recent and Ongoing Developments

Mejı́a-Rodrı́guez

Aprà

Autschbach

et al. 2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…To improve the accuracy of APDFT, assuming convergence, the perturbation expansion order must be increased. Analytic derivatives of energy and electron density ,− allow numerically stable yet computationally efficient evaluations of higher-order APDFT. Finite differences are also useful for systematically increasing the expansion order. ,, A hybrid approach of high- and low-level reference theories for the derivatives of the electron density is effective in reducing the computational cost of higher-order APDFT calculations .…”

Section: Computational Detailsmentioning

confidence: 99%

Optimization of General Molecular Properties in the Equilibrium Geometry Using Quantum Alchemy: An Inverse Molecular Design Approach

Shiraogawa

Hasegawa

2023

J. Phys. Chem. A

View full text Add to dashboard Cite

Inverse molecular design allows the optimization of molecules in chemical space and is promising for accelerating the development of functional molecules and materials. To design realistic molecules, it is necessary to consider geometric stability during optimization. In this work, we introduce an inverse design method that optimizes molecular properties by changing the chemical composition in the equilibrium geometry. The optimization algorithm of our recently developed molecular design method has been modified to allow molecular design for general properties at a low computational cost. The proposed method is based on quantum alchemy and does not require empirical data. We demonstrate the applicability and limitations of the present method in the optimization of the electric dipole moment and atomization energy in small chemical spaces for (BF, CO), (N2, CO), BN-doped benzene derivatives, and BN-doped butane derivatives. It was found that the optimality criteria scheme adopted for updating the molecular species yields faster convergence of the optimization and requires a less computational cost. Moreover, we also investigate and discuss the applicability of quantum alchemy to the electric dipole moment.

show abstract

“…[80][81][82] In this section, we demonstrate how APDFT can be used to predict protonation and deprotonation energies accurately. APDFT3 error for vertical deprotonation energies can be as small as 1.4 kcal/mol 25,26,40,83 , we would like to go beyond the fixed geometry approximation including the geometrical relaxation energy. More specifically, we exemplify our approach for the alchemical navigation of the iso-electronic 10 electron series of second row hydrides CH 4 →NH 3 →H 2 O→ HF,(see figure 5 for illustration).…”

Section: Alchemical Protonation and Deprotonationmentioning

confidence: 99%

Alchemical geometry relaxation

Domenichini¹,

Lilienfeld²

2022

Preprint

View full text Add to dashboard Cite

We propose to relax geometries throughout chemical compound space (CCS) using alchemical perturbation density functional theory (APDFT). APDFT refers to perturbation theory involving changes in nuclear charges within approximate solutions to Schrödinger's equation. We give an analytical formula to calculate the mixed second order energy derivatives with respect to both, nuclear charges and nuclear positions (named "alchemical force"), within the restricted Hartree-Fock case. We have implemented and studied the formula for its use in geometry relaxation of various reference and target molecules. We have also analysed the convergence of the alchemical force perturbation series, as well as basis set effects. Interpolating alchemically predicted energies, forces, and Hessian to a Morse potential yields more accurate geometries and equilibrium energies than when performing a standard Newton Raphson step. Our numerical predictions for small molecules including BF, CO, N2, CH 4 , NH 3 , H 2 O, and HF yield mean absolute errors of of equilibrium energies and bond lengths smaller than 10 mHa and 0.01 Bohr for 4 th order APDFT predictions, respectively. Our alchemical geometry relaxation still preserves the combinatorial efficiency of APDFT: Based on a single coupled perturbed Hartree Fock derivative for benzene we provide numerical predictions of equilibrium energies and relaxed structures of all the 17 iso-electronic charge-netural BN-doped mutants with averaged absolute deviations of ∼27 mHa and ∼0.12 Bohr, respectively.

show abstract

Analytic Alchemical Derivatives for the Analysis of Differential Acidity Assisted by the h Function

Cited by 7 publications

References 74 publications

NWChem: Recent and Ongoing Developments

NWChem: Recent and Ongoing Developments

Optimization of General Molecular Properties in the Equilibrium Geometry Using Quantum Alchemy: An Inverse Molecular Design Approach

Alchemical geometry relaxation

Contact Info

Product

Resources

About