Analytical First Derivatives of the <scp>SCF</scp> Energy for the Conductor‐Like Polarizable Continuum Model With Non‐Static Radii

2025/04/24 by Lukas Wittmann, Miquel García‐Ratés, Christoph Riplinger · 1 voice · 1 citation
Physics and Astronomy · Chemistry · #Advanced Chemical Physics Studies #Advanced NMR Techniques and Applications #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.1002/jcc.70099

Abstract

Within this work, we present the derivation and implementation of analytical gradients for the Gaussian-switching (SwiG) Conductor-like Polarizable Continuum Model (CPCM) with general nuclear coordinate-dependent non-static radii used for the creation of van der Waals-type cavities. This is done using the recently presented dynamic radii adjustment for continuum solvation (Draco) scheme. This allows for efficient geometry optimization and reasonable numerical Hessian calculations. The derived gradient is implemented in ORCA, and therefore is easily applicable. The derivation and implementation is validated by comparing analytical and numerical gradients and testing geometry optimizations on a diverse test set, including small organic compounds, metal-organic complexes, and highly charged species. We additionally test the continuity of the potential energy surface using an example where very strong changes in the radii occur. The computational efficiency of the derived gradient is investigated.

Citations

• A generally applicable atomic-charge dependent London dispersion correction
• r2SCAN-3c: A “Swiss army knife” composite electronic-structure method
• An improved chain of spheres for exchange algorithm
• CREST—A program for the exploration of low-energy molecular chemical space

Cited by

• Notizen aus der Forschung

Discussions

• We’ve derived and implemented analytical SCF energy gradients for the conductor-like polarizable continuum model with non-static radii. Another fruitful collaboration with @faccts.de! 🔗 doi.org/10. [bsky, 10 points, 0 comments]

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