Calculating vibrational excitation energies using tensor-decomposed vibrational coupled-cluster response theory

Madsen, N.; Jensen, Rasmus Berg; Christiansen, Ove

doi:10.1063/5.0037240

Cited by 5 publications

(3 citation statements)

References 69 publications

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“…This representation has been used for nearly 20 years by a number of research groups; a sample of these are refs , , , and − . It continues to be actively used in a variety of applications and theoretical developments. − In MULTIMODE the maximum value of n is 6. However, from numerous tests it appears that a 4MR typically gives energies that are converged to within roughly 1–5 cm –1 . − Thus, we generally use 4MR with an existing full-dimensional PES, and this is also done here.…”

Section: Methodsmentioning

confidence: 99%

MULTIMODE Calculations of Vibrational Spectroscopy and 1d Interconformer Tunneling Dynamics in Glycine Using a Full-Dimensional Potential Energy Surface

Houston

Conte

et al. 2021

J. Phys. Chem. A

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A full-dimensional, permutationally invariant polynomial potential energy surface for glycine recently reported (R. Conte et al., J. Chem. Phys. 2020, 153, 244301) is used with the code MULTIMODE to determine the IR absorption spectra for Conformers I and II using a new separable dipole moment function. The calculated spectra agree well with the experimental ones. The full-dimensional nature of the potential allows us also to examine dynamical results, such as tunneling rates. Remarkably, using a onedimensional path based on the potential energy surface to estimate the tunneling rate from Conformer VI to Conformer I, good agreement is found with the recent experimental measurement. Finally a brief comparison of our potential energy surface with a recently reported sGDML one is made.

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Section: Methodsmentioning

confidence: 99%

MULTIMODE Calculations of Vibrational Spectroscopy and 1d Interconformer Tunneling Dynamics in Glycine Using a Full-Dimensional Potential Energy Surface

Houston

Conte

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…This representation has been used for nearly 20 years by a number of research groups; a sample of these are refs − and − . It continues to be actively used in a variety of applications and theoretical developments. − In MULTIMODE the maximum value of n is 6. However, from numerous tests it appears that a 4MR typically gives energies that are converged to within roughly 1–5 cm –1 . − Thus, we generally use 4MR with an existing full-dimensional PES and this is also done here.…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

Semiclassical and VSCF/VCI Calculations of the Vibrational Energies of trans- and gauche-Ethanol Using a CCSD(T) Potential Energy Surface

Conte

Nandi

Qu³

et al. 2022

J. Phys. Chem. A

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A recent full-dimensional Δ-Machine learning potential energy surface (PES) for ethanol is employed in semiclassical and vibrational self-consistent field (VSCF) and virtual-state configuration interaction (VCI) calculations, using MULTIMODE, to determine the anharmonic vibrational frequencies of vibration for both the trans and gauche conformers of ethanol. Both semiclassical and VSCF/VCI energies agree well with the experimental data. We find significant mixing between the VSCF basis states due to Fermi resonances between bending and stretching modes. The same effects are also accurately described by the full-dimensional semiclassical calculations. These are the first high-level anharmonic calculations using a PES, in particular a "gold-standard" CCSD(T) one.

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“…This includes approaches based on permutationally invariant polynomials, Gaussian processes, − and neural networks,. − However, the computational cost associated with the exact solution of the resulting vibrational Schrödinger equation scales exponentially with system size, prohibiting straightforward calculations for molecules with more than a dozen degrees of freedom. The design of novel anharmonic methods to tame this unfavorable scaling remains an active field of research. − Among the vibrational structure methods developed, techniques leveraging so-called tensor-network-based algorithms are particularly promising. − The most commonly applied tensor-based algorithm in electronic structure theory has been the density matrix renormalization group (DMRG), , which allows for an efficient deterministic variational optimization of wave functions represented as matrix product states (MPSs). − In previous work, we introduced the vibrational DMRG (vDMRG) algorithm, , which enables large-scale vibrational structure calculations of anharmonic systems described by Taylor-expanded PESs.…”

Section: Introductionmentioning

confidence: 99%

Flexible DMRG-Based Framework for Anharmonic Vibrational Calculations

Glaser,

Baiardi,

Reiher

2023

J. Chem. Theory Comput.

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We present a novel formulation of the vibrational density matrix renormalization group (vDMRG) algorithm tailored to strongly anharmonic molecules described by general, high-dimensional model representations of potential energy surfaces. For this purpose, we extend the vDMRG framework to support vibrational Hamiltonians expressed in the so-called n -mode second-quantization formalism. The resulting n -mode vDMRG method offers full flexibility with respect to both the functional form of the PES and the choice of the single-particle basis set. We leverage this framework to apply, for the first time, vDMRG based on an anharmonic modal basis set optimized with the vibrational self-consistent field algorithm on an on-the-fly constructed PES. We also extend the n -mode vDMRG framework to include excited-state-targeting algorithms in order to efficiently calculate anharmonic transition frequencies. We demonstrate the capabilities of our novel n -mode vDMRG framework for methyloxirane, a challenging molecule with 24 coupled vibrational modes.

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Calculating vibrational excitation energies using tensor-decomposed vibrational coupled-cluster response theory

Abstract: Calculating vibrational excitation energies using tensor-decomposed vibrational coupledcluster response theory", J. Chem. Phys. 154, 054113 (2021)) and may be found at (

Cited by 5 publications

References 69 publications

MULTIMODE Calculations of Vibrational Spectroscopy and 1d Interconformer Tunneling Dynamics in Glycine Using a Full-Dimensional Potential Energy Surface

MULTIMODE Calculations of Vibrational Spectroscopy and 1d Interconformer Tunneling Dynamics in Glycine Using a Full-Dimensional Potential Energy Surface

Semiclassical and VSCF/VCI Calculations of the Vibrational Energies of trans- and gauche-Ethanol Using a CCSD(T) Potential Energy Surface

Flexible DMRG-Based Framework for Anharmonic Vibrational Calculations

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