Tailored coupled cluster method with sample-based quantum diagonalization: Application to titanium-based metallocene catalytic reactions for 1-hexene production
Abstract
Sample-based quantum diagonalization (SQD) is a hybrid quantum-classical method for electronic-structure calculations. We applied SQD to a titanium-based metallocene catalyst system for 1-hexene production, where free-energy differences must be predicted within 1 kcal/mol to accurately determine product selectivity. However, currently accessible active spaces on quantum computers are limited in size, leaving significant dynamical correlation effects outside the active space. To address this challenge, we combined SQD with Tailored Coupled Cluster (TCC) theory. In this SQD-TCC framework, static correlation is treated by SQD, while dynamical correlation is incorporated through CCSD and its perturbative triples extension, TCC(T). We calculated the relative energies of two transition states governing 1-hexene selectivity. While SQD alone did not yield converged relative energies within practically accessible active spaces, SQD-TCC and SQD-TCC(T) provided reasonably converged results. Importantly, the relative energy obtained from SQD-TCC(T) differed by more than 1 kcal/mol from the corresponding CCSD(T) result, demonstrating the significance of static correlation in this system and its impact on predicted selectivity. Although TCC(T) calculations based on CASCI are feasible for small active spaces, the present system requires substantially larger active spaces that are beyond the reach of CASCI. By using SQD, we were able to access active spaces impractical for classical CASCI calculations. These results demonstrate that both static and dynamical electron correlation are essential for a reliable description of this chemistry and highlight the importance of incorporating dynamical correlation into quantum-computing approaches targeting chemically accurate simulations.
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BibTeX
@misc{lin2026tailored,
title = {{Tailored coupled cluster method with sample-based quantum diagonalization: Application to titanium-based metallocene catalytic reactions for 1-hexene production}},
author = {Tzu-Wei Lin and Hirotoshi Hirai and Kuan-Chieh Huang and Zih-Chao Hong and Hui-Zhong Zhuang and Tsung-Hui Li},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.16558},
eprint = {2609.16558},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.16558},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Tailored coupled cluster method with sample-based quantum diagonalization: Application to titanium-based metallocene catalytic reactions for 1-hexene production
AU - Tzu-Wei Lin
AU - Hirotoshi Hirai
AU - Kuan-Chieh Huang
AU - Zih-Chao Hong
AU - Hui-Zhong Zhuang
AU - Tsung-Hui Li
PY - 2026
DA - 2026/09/17
PB - arXiv
DO - 10.48550/arxiv.2609.16558
UR - https://arxiv.org/abs/2609.16558
AB - Sample-based quantum diagonalization (SQD) is a hybrid quantum-classical method for electronic-structure calculations. We applied SQD to a titanium-based metallocene catalyst system for 1-hexene production, where free-energy differences must be predicted within 1 kcal/mol to accurately determine product selectivity. However, currently accessible active spaces on quantum computers are limited in size, leaving significant dynamical correlation effects outside the active space. To address this challenge, we combined SQD with Tailored Coupled Cluster (TCC) theory. In this SQD-TCC framework, static correlation is treated by SQD, while dynamical correlation is incorporated through CCSD and its perturbative triples extension, TCC(T). We calculated the relative energies of two transition states governing 1-hexene selectivity. While SQD alone did not yield converged relative energies within practically accessible active spaces, SQD-TCC and SQD-TCC(T) provided reasonably converged results. Importantly, the relative energy obtained from SQD-TCC(T) differed by more than 1 kcal/mol from the corresponding CCSD(T) result, demonstrating the significance of static correlation in this system and its impact on predicted selectivity. Although TCC(T) calculations based on CASCI are feasible for small active spaces, the present system requires substantially larger active spaces that are beyond the reach of CASCI. By using SQD, we were able to access active spaces impractical for classical CASCI calculations. These results demonstrate that both static and dynamical electron correlation are essential for a reliable description of this chemistry and highlight the importance of incorporating dynamical correlation into quantum-computing approaches targeting chemically accurate simulations.
ER -