Tunnelling splitting patterns in some partially deuterated water trimers

Eraković, Mihael; Cvitaš, Marko T.

doi:10.1039/d0cp06135b

Cited by 6 publications

(16 citation statements)

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“…The bifurcation splitting patterns in PD water trimers HDO(H 2 O) 2 and D 2 O(H 2 O) 2 have been determined in experiments 13 and by us using the instanton theory. 14 …”

Section: Introductionmentioning

confidence: 99%

“…The method was applied to calculate TSs in excited vibrational states of malonaldehyde 55 with the asymmetric isotopic substitutions using a fit of model potential parameters to quantum-chemical data. The extensions of the RPI and JFI methods to the ground-states of the asymmetric systems with a weak bias have recently been derived and applied to PD malonaldehyde 9 and the water trimer, 14 respectively.…”

Section: Introductionmentioning

confidence: 99%

“…Further examples of the mixing have been studied in the HF–DF dimer and PD vinyl radical, CHD–CH, using full-dimensional exact calculations. The bifurcation splitting patterns in PD water trimers HDO(H 2 O) 2 and D 2 O(H 2 O) 2 have been determined in experiments and by us using the instanton theory …”

Section: Introductionmentioning

confidence: 99%

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Vibrational Tunneling Spectra of Molecules with Asymmetric Wells: A Combined Vibrational Configuration Interaction and Instanton Approach

Eraković

Cvitaš

2022

J. Chem. Theory Comput.

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A combined approach that uses the vibrational configuration interaction (VCI) and semiclassical instanton theory was developed to study vibrational tunneling spectra of molecules with multiple wells in full dimensionality. The method can be applied to calculate low-lying vibrational states in the systems with an arbitrary number of minima, which are not necessarily equal in energy or shape. It was tested on a two-dimensional double-well model system and on malonaldehyde, and the calculations reproduced the exact quantum mechanical (QM) results with high accuracy. The method was subsequently applied to calculate the vibrational spectrum of the asymmetrically deuterated malonaldehyde with nondegenerate vibrational frequencies in the two wells. The spectrum is obtained at a cost of single-well VCI calculations used to calculate the local energies. The interactions between states of different wells are computed semiclassically using the instanton theory at a comparatively negligible computational cost. The method is particularly suited to systems in which the wells are separated by large potential barriers and tunneling splittings are small, for example, in some water clusters, when the exact QM methods come at a prohibitive computational cost.

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“…The bifurcation splitting patterns in PD water trimers HDO(H 2 O) 2 and D 2 O(H 2 O) 2 have been determined in experiments 13 and by us using the instanton theory. 14 …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational Tunneling Spectra of Molecules with Asymmetric Wells: A Combined Vibrational Configuration Interaction and Instanton Approach

Eraković

Cvitaš

2022

J. Chem. Theory Comput.

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“…Further examples of the mixing have been studied in HF−HD dimer 11 and partially deuterated vinyl radical 12 , CHD−CH, using full-dimensional exact calculations. The splitting pattern in partially deuterated water trimers HDO(H 2 O) 2 and D 2 O(H 2 O) 2 have been determined in experiment 13 and by us using instanton theory 14 .…”

Section: Introductionmentioning

confidence: 99%

“…The method was applied to calculate TSs in excited vibrational states of malonaldehyde 55 with the asymmetric isotopic substitutions using a fit of model potential parameters to quantum-chemical data. The extensions of the RPI and JFI method to the groundstates of the asymmetric systems with a weak bias have recently been derived and applied to partially deuterated malonaldehyde 9 and water trimer 14 , respectively.…”

Section: Introductionmentioning

confidence: 99%

Vibrational tunneling spectra of molecules with asymmetric wells: a combined vibrational configuration interaction and instanton approach

Eraković¹,

Cvitaš²

2022

Preprint

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A combined approach that uses the vibrational configuration interaction (VCI) and semiclassical instanton theory was developed to study vibrational tunneling spectra of molecules with multiple wells in full dimensionality. The method can be applied to calculate low-lying vibrational states in the systems with arbitrary number of minima, which are not necessarily equal in energy or shape. It was tested on a two-dimensional double-well model system and on malonaldehyde and the calculations reproduced the exact quantum-mechanical results with high accuracy. The method was subsequently applied to calculate vibrational spectrum of the asymmetrically deuterated malonaldehyde with non-degenerate vibrational frequencies in the two wells. The spectrum is obtained at a cost of single-well VCI calculations used to calculate the local energies. The interactions between states of different wells are computed semiclassically using instanton theory at a comparatively negligible computational cost. The method is particularly suited to systems in which the wells are separated by large potential barriers and tunneling splittings are small, e.g, in some water clusters, when the exact quantum-mechanical methods come at a prohibitive computational cost.

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A fluxional anionic water trimer

Finn

Baletto²

2022

Frontiers of Nanoscience

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Tunnelling splitting patterns in some partially deuterated water trimers

Abstract: We apply our recently developed semiclassical method for calculating tunnelling spittings (TS) in asymmetric systems to make the first characterization of the ground-state TS pattern of some partially deuterated water...

Cited by 6 publications

References 75 publications

Vibrational Tunneling Spectra of Molecules with Asymmetric Wells: A Combined Vibrational Configuration Interaction and Instanton Approach

Vibrational Tunneling Spectra of Molecules with Asymmetric Wells: A Combined Vibrational Configuration Interaction and Instanton Approach

Vibrational tunneling spectra of molecules with asymmetric wells: a combined vibrational configuration interaction and instanton approach

A fluxional anionic water trimer

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