Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states

Fuente: arXiv
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Main Author: Larsson, Henrik R.
Format: Preprint
Published: 2025
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author Larsson, Henrik R.
author_facet Larsson, Henrik R.
contents Accurate vibrational spectra are essential for understanding how molecules behave, yet their computation remains challenging and benchmark data to reliably compare different methods are sparse. Here, we present high-accuracy eigenstate computations for the six-atom, 12-dimensional acetonitrile molecule, a prototypical, strongly coupled, anharmonic system. Using a density matrix renormalization group (DMRG) algorithm with a tree-tensor-network-state (TTNS) ansatz, a refinement using TTNSs as basis set, and reliable procedures to estimate energy errors, we compute up to 5,000 vibrational states with error estimates below 0.0007 $\mathrm{cm}^{-1}$. Our analysis reveals that previous works underestimated the energy error by up to two orders of magnitude. Our data serve as a benchmark for future vibrational spectroscopy methods and our new method offers a path toward similarly precise computations of large, complex molecular systems.
format Preprint
id arxiv_https___arxiv_org_abs_2504_05382
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states
Larsson, Henrik R.
Chemical Physics
Computational Physics
Accurate vibrational spectra are essential for understanding how molecules behave, yet their computation remains challenging and benchmark data to reliably compare different methods are sparse. Here, we present high-accuracy eigenstate computations for the six-atom, 12-dimensional acetonitrile molecule, a prototypical, strongly coupled, anharmonic system. Using a density matrix renormalization group (DMRG) algorithm with a tree-tensor-network-state (TTNS) ansatz, a refinement using TTNSs as basis set, and reliable procedures to estimate energy errors, we compute up to 5,000 vibrational states with error estimates below 0.0007 $\mathrm{cm}^{-1}$. Our analysis reveals that previous works underestimated the energy error by up to two orders of magnitude. Our data serve as a benchmark for future vibrational spectroscopy methods and our new method offers a path toward similarly precise computations of large, complex molecular systems.
title Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states
topic Chemical Physics
Computational Physics
url https://arxiv.org/abs/2504.05382