Symmetry-Match Fraction for Active-Space Selection: A Simple Route to Accurate Reaction Energies in VQE/UCCSD

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Authors: Maitreyee Sarkar, Lisa Roy, Akash Popat Gutal, Atul Kumar, Manikandan Paranjothy
Cited by: 1
References: 35

Abstract

Simulation of chemical reactions to compute reaction energies using variational algorithms remains challenging in achieving chemical accuracy relative to benchmark computational chemistry methods due to limitations such as qubit number, circuit depth, and noise. To address this issue, we propose the definition of different active spaces for studying chemical reactions, incorporating irreducible representations of both ground and excited states by defining the maximum contribution of excitation terms in the ansatz, implemented here within a second-order Trotterized UCCSD-VQE framework. Our results demonstrate that this approach can achieve chemical accuracy for several representative reactions and yields close agreement with benchmark methods across a broader range of reactions. For all reactions studied, the difference in reaction energies between VQE and CCSD remains within 1 kcal/mol. At the same time, comparison with FCI shows chemical accuracy for several cases and close agreement for the remaining systems. Furthermore, our analysis simplifies the selection of active spaces and electrons for each reaction, reducing it to a single optimal combination that supports chemically accurate or near-chemical-accuracy predictions.

Fields of Study & Subjects

Machine Learning in Materials Science Advanced Chemical Physics Studies Spectroscopy and Quantum Chemical Studies

Publication details

Journal / source
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Volume
130
Issue
28
Pages
5594–5601
Publication date
9 June 2026
Language
EN