English

Topological resolution of conical intersection seams and the coupled cluster bifurcation via mixed Hodge modules

Chemical Physics 2025-12-24 v1 Mathematical Physics math.MP Computational Physics Quantum Physics

Abstract

The rigorous description of Conical Intersections (CIs) remains the central challenge of non-adiabatic quantum chemistry. While the ``Yarkony Seam'' -- the (3N8)(3N-8)-dimensional manifold of degeneracy -- is well-understood geometrically, its accurate characterization by high-level electronic structure methods is plagued by numerical instabilities. Specifically, standard Coupled Cluster (CC) theory suffers from root bifurcations near Ground State CIs, rendering the ``Gold Standard'' of chemistry inapplicable where it is needed most. Here, we present \textbf{QuMorpheus}, an open-source computational package that resolves these singularities by implementing a topological framework based on Dissipative Mixed Hodge Modules (DMHM) [P. Saurabh, arXiv:2512.19487 (2025)]. By algorithmically mapping the CC polynomial equations to a spectral sheaf, we compute the exact Monodromy (μ\mu) invariants of the intersection. We demonstrate that this automated algebraic geometry approach correctly identifies the physical ground state topology in the K\"{o}hn-Tajti model and resolves the intersection seams of realistic chemical systems, including Ethylene and the Chloronium ion (H2Cl+\mathrm{H_2Cl^+}). Furthermore, we apply QuMorpheus to the photoisomerization of Previtamin D, proving that the experimentally observed Woodward-Hoffmann selection rules are a direct consequence of a topological ``Monodromy Wall'' (μ=1,γ=π\mu=1, \gamma=\pi) rather than purely energetic barriers. This establishes a general software solution to the ``Yarkony Problem,'' enabling the robust, automated mapping of global intersection seams in complex molecular systems. The topological stability of these intersections allows for the control protocols discussed in Ref.[P. Saurabh, Submitted to Phys. Rev. X (2025)].

Keywords

Cite

@article{arxiv.2512.20414,
  title  = {Topological resolution of conical intersection seams and the coupled cluster bifurcation via mixed Hodge modules},
  author = {Prasoon Saurabh},
  journal= {arXiv preprint arXiv:2512.20414},
  year   = {2025}
}

Comments

12 pages, 5 figures. Includes Supplementary Information. Code available at https://github.com/prasoon-s/QuMorpheus