Resolving the ground state intersection problem in coupled cluster theory
Abstract
A physically correct description of ground state conical intersections is essential for simulating non-adiabatic dynamics of radiationless decay to the electronic ground state. Coupled cluster theory offers a particularly balanced treatment of static and dynamic correlation in excited states. However, coupled cluster methods and other single-reference approaches fail to describe ground state intersection regions, and several workarounds have been proposed to address this shortcoming. Here we present convex similarity constrained coupled cluster theory (CVX-SCC), a framework that resolves the ground state intersection problem by construction. We have applied this theory to two different coupled cluster methods, and tested the resulting models on ethylene, uracil, PSB3, and HeH2, showing that both variants produce physically correct ground state conical intersections. With future development of nuclear gradients and non-adiabatic coupling vectors, this approach will provide single-reference electronic structures suitable for non-adiabatic dynamics simulations all the way to the ground state.
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BibTeX
@misc{stoll2026resolving,
title = {{Resolving the ground state intersection problem in coupled cluster theory}},
author = {Leo Stoll and Federico Rossi and Henrik Koch},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.10164},
eprint = {2609.10164},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.10164},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Resolving the ground state intersection problem in coupled cluster theory
AU - Leo Stoll
AU - Federico Rossi
AU - Henrik Koch
PY - 2026
DA - 2026/09/09
PB - arXiv
DO - 10.48550/arxiv.2609.10164
UR - https://arxiv.org/abs/2609.10164
AB - A physically correct description of ground state conical intersections is essential for simulating non-adiabatic dynamics of radiationless decay to the electronic ground state. Coupled cluster theory offers a particularly balanced treatment of static and dynamic correlation in excited states. However, coupled cluster methods and other single-reference approaches fail to describe ground state intersection regions, and several workarounds have been proposed to address this shortcoming. Here we present convex similarity constrained coupled cluster theory (CVX-SCC), a framework that resolves the ground state intersection problem by construction. We have applied this theory to two different coupled cluster methods, and tested the resulting models on ethylene, uracil, PSB3, and HeH_2, showing that both variants produce physically correct ground state conical intersections. With future development of nuclear gradients and non-adiabatic coupling vectors, this approach will provide single-reference electronic structures suitable for non-adiabatic dynamics simulations all the way to the ground state.
ER -