Efficient and reliable identification and optimization of transition state structures is a longstanding challenge in computational chemistry. Popular chain-of-states methods require hundreds if not thousands of ab initio calculations to generate initial guesses for local quasi-Newton optimizers, with persistent risk of collapse to an alternative stationary point on the potential energy surface (PES). Here, we show that high-quality guess structures for transition state optimization can be obtained by constructing the geodesic path between reactant and product structures on the PES generated by machine learning potentials (MLPs). We present an algorithm for optimization of such geodesic paths, as well as the associated codebase. We demonstrate effectiveness of this approach using the recent eSEN-sm-cons MLP. On average, the highest-energy point along these MLP geodesics requires 30% fewer quasi-Newton optimization steps to converge to the transition state compared to guesses from the fully ab initio freezing string method. Our approach therefore completely eliminates the need for ab initio calculations for the generation of transition state guesses and considerably speeds up subsequent structural optimization. Geodesic construction on ML PES thus promises to be a useful approach for efficient computational elucidation of complex chemical reaction networks.

One approach to calculating electronic excited states treats both ground and excited states as single determinants, either by direct optimization or with the aid of constraints. In this work, we exten...

We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to shortcomings in the underlying linear response method, with final results from less accurate starting points nearly as good as those from the best starting points. This pattern is especially stark in charge transfer states, where the approach converts starting points with multi-eV errors into post-linear-response results with errors on the order of 0.1 eV. These findings highlight the ability of Aufbau suppressed coupled cluster to perform its own orbital relaxations and raise the question of whether initializing it with an orbital relaxed reference is worth the trouble.

Progress in the fundamental understanding of the chirality-induced spin-selectivity (CISS) effect is hindered by complexity of the systems that have been characterized experimentally. With the goal of...

2024-2025 Diversity Enhancement Faculty Award This award recognizes a faculty member from within The Ohio State University College of Arts and Sciences whose research, teaching and/or service/outreach...

The symmetry breaking in octahedral silsesquioxane and its germanium analogues (Si8O12H8 and Ge8O12H8) has been investigated using the M06-2X/6-31++G(3df, 3pd) method and group theory. Both structures...

Exciton coupling in organic chromophores is revisited through the lens of the transition density. The presented formalism gives insight into the strength and sign of the coupling based on the relativ...