Variational analysis of HF dimer tunneling rotational spectra using an ab initio potential energy surface

Polyansky, Oleg L.; Ovsyannikov, Roman I.; Tennyson, Jonathan; Белов, С. П.; Tretyakov, M.Yu.; Makhnev, Vladimir Yu.; Zobov, Nikolai F.

doi:10.1016/j.jms.2021.111481

Cited by 2 publications

(8 citation statements)

References 44 publications

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“…Table VII shows the distance between the K=3, 4, 5 levels of the (0000) and (0010) vibrational states and neighboring levels above and below the levels in question. The close positions of the interacting levels which move the energy levels of the K = 3 (0000) branch have been noted previously 1 and are shown in the Table VII. The B constants for the K= 0 -5 (0000) and (0010) vibrational states presented in Table IX display different behavior for different vibrational states.…”

Section: Rotational B Constantssupporting

confidence: 80%

“…Therefore, the parameters of the basis functions for (DF) 2 were changed (r: w e =4500, R: w e =15.48), so a Constants calculated from ν4 constants determined in Ref. [ 1]and values for ∆X (X = B, D) in Ref. [ 8] Description of headings: p1: Variational calculations using potential from Huang et al 3 ; P: Polynomial fit of ab initio points from this work; M: Morse-fit of ab initio points from this work; K: Morse-fit plus higher-order correlation, K = M + CCSDT(Q)-CCSD(T)/aug-cc-pVTZ; CV: Morse-fit plus higher-order correlation plus core-valence, CV = K + CCSD(T)/cc-pCV6Z; DBOC: CV plus scalar relativistic and adiabatic correction, CV + CCSD/aug-cc-pCVTZ + CCSD(T)/aug-cc-pV5Z; pall: polynomial fit with all listed above corrections included.…”

Section: Df Dimermentioning

confidence: 99%

“…However, there is another important motivation for accurate studies of (HF) 2 . The similarity between the HF and water dimers, which was described in detail in our previous study, 1 means one can use the HF-dimer observed minus calculated discrepancies to provide an estimates for the corresponding water dimer discrepancies for calculations performed at a similar level of ab initio theory. This is important because the HF dimer is one of the few molecular complexes for which gas-phase high resolution spectra exist which means that observed minus calculated discrepancies can be characterised for the highly excited rotational K states of (HF) 2 .…”

Section: Introductionmentioning

confidence: 95%

“…Information on states with K > 4 was not obtained in these FIR publications either. Another limitation on analyzing the inversion-rotation spectrum caused by the accuracy of our calculations is the inability to fix definitive J values to the v 4 = 1 branch newly assigned in 1 .…”

Section: Introductionmentioning

confidence: 99%

“…The value of B and ∆ K are defined for example in the Refs. 1,4 and are determined from the experimental frequencies using the equation…”

Section: Introductionmentioning

confidence: 99%

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Highly accurate HF dimer ab initio potential energy surface

Ovsyannikov

Makhnev

Zobov

et al. 2022

The Journal of Chemical Physics

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A very accurate, (HF)$_2$ potential energy surface (PES)is constructed based on \ai\ calculations performed% at the CCSD(T) level of theory with an aug-cc-pVQZ-F12basis set at about 152~000 points.A higher correlation correction is computed at CCSDT(Q) level for 2000 points and is considered alongside other more minorcorrections due to relativity, core-valence correlation and Born-Oppenheimer failure.The analytical surface constructed uses 500 constants to reproduce the \ai\ points with a standard deviation of 0.3 \cm.Vibration-rotation-inversion energy levels of the HF dimer are computed for this PES by variational solution of the nuclear-motionSchr\"{o}dinger using program WAVR4. Calculations over an extended range of rotationally excited states show very good agreementwith the experimental data. In particular the known empirical rotational constants $B$ for the ground vibrational states are predicted to better than about 2 MHz.$B$ constants for excited vibrational states are reproduced several times more accurately than by previous calculations. %The experimental dissociation energy of the HF dimer is reproduced \ai\ within the experimental accuracy of about 1 \cm\ for the first time. This level of accuracy is shown to extend to higher excited inter-molecular vibrational states $v$ and higher excited rotational quantum numbers $(J,K_a)$.

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Section: Rotational B Constantssupporting

confidence: 80%

Section: Df Dimermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

“…The value of B and ∆ K are defined for example in the Refs. 1,4 and are determined from the experimental frequencies using the equation…”

Section: Introductionmentioning

confidence: 99%

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Highly accurate HF dimer ab initio potential energy surface

Ovsyannikov

Makhnev

Zobov

et al. 2022

The Journal of Chemical Physics

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Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster

Hippler

Oeltjen

Qüack

2023

Israel Journal of Chemistry

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Rovibrationally resolved spectra of the Nj=22, Ka=0←1 transition and of the Nj=23, Ka=0←0 and Ka=1←0 transitions of the hydrogen‐bonded (HF)2 have been measured in the near infrared range near 1.3 μm by cw‐diode laser cavity ring‐down spectroscopy in a pulsed supersonic slit jet expansion. The spectroscopic assignment and analysis provided an insight into the dynamics of these highly‐excited vibrational states, in particular concerning the predissociation of the hydrogen bond and the tunneling process of the hydrogen bond switching. Together with our previously analyzed spectra of the Nj=21 and Nj=22 components, the mode‐specific dynamics in all three components of this triad can now be compared. In the N=2 triad, the HF‐stretching vibration is excited by two quanta with similar excitation energy, but the quanta are distributed in three different ways, which has a distinct influence on the dynamics. The observed band centers and tunneling splittings are in agreement with our recent calculations on the (HF)2 potential energy hypersurface SO‐3, resolving the long‐standing discussion about the symmetry ordering of polyad levels in this overtone region. The results are also discussed in relation to the general questions of non‐statistical reaction dynamics of polyatomic molecules and clusters and in relation to quasi‐adiabatic channel above barrier tunneling.

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Variational analysis of HF dimer tunneling rotational spectra using an ab initio potential energy surface

Cited by 2 publications

References 44 publications

Highly accurate HF dimer ab initio potential energy surface

Highly accurate HF dimer ab initio potential energy surface

Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster

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Variational analysis of HF dimer tunneling rotational spectra using an ab initio potential energy surface

Cited by 2 publications

References 44 publications

Highly accurate HF dimer ab initio potential energy surface

Highly accurate HF dimer ab initio potential energy surface

Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)2Cluster

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Mode‐Selective Vibrational‐Tunneling Dynamics in theN=2 Triad of the Hydrogen‐Bonded (HF)₂Cluster