Accurate calculations of bound rovibrational states for argon trimer

Brandon, Drew T.; Poirier, Bill

doi:10.1063/1.4887459

Cited by 13 publications

(8 citation statements)

References 62 publications

(105 reference statements)

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“…The number of iterations is about 500 in the QMR procedure, and about 100 in the Lanczos procedure. The PIST method has been applied in various cases and applications. − This scheme is very efficient, for instance, it costs less than 1 h to converge the required states in our largest scale calculations with basis set of 359 592 functions on our workstation with Xeon Silver 4210.…”

Section: Theory and Methodsmentioning

confidence: 99%

Efficient Quantum Mechanical Calculations of Mode-Specific Tunneling Splittings upon Fundamental Excitation in the Dimer of Formic Acid

2020

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The formic acid dimer (FAD) is an important benchmark system for understanding the double hydrogen transfer process. Most recently, Zhang et al. measured a few tunneling splittings upon fundamental excitation of FAD precisely (Zhang, Y. et al. J. Chem. Phys. 2017, 146, 244306); however, relevant theoretical studies are very limited. Here, we present a multidimensional quantum dynamics study on mode-specific tunneling splittings upon fundamental excitation in FAD with an efficient theoretical scheme developed by our group in which the process-oriented basis function customization strategy is combined with the preconditioned inexact spectral transform method. Various mode-specific tunneling splittings upon fundamental excitation are systematically calculated, and interesting mode-specific excitation effects on tunneling rate are identified. In particular, the calculated tunneling splittings for the ν 22 and ν 21 states are in good agreement with experiment, and the remarkable mode-specific suppression effects upon excitation should result from that the antisymmetric vibrational modes hinder the concerted double H-transfer. The present work is helpful to acquire a better understanding of the mode-specific excitation effects on tunneling processes. Article pubs.acs.org/JPCA

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Section: Theory and Methodsmentioning

confidence: 99%

Efficient Quantum Mechanical Calculations of Mode-Specific Tunneling Splittings upon Fundamental Excitation in the Dimer of Formic Acid

2020

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“…However, loosening it too much will highly increase the number of steps for Lanczos iteration, which is much slower than QMR iteration. The PIST method has also been employed in other applications (Bian and Poirier, 2004; Li and Bian, 2008; Brandon and Poirier, 2014; Petty and Poirier, 2014).…”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Double Proton Transfer in the Dimer of Formic Acid: An Efficient Quantum Mechanical Scheme

2019

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Double proton transfer plays an important role in biology and chemistry, such as with DNA base pairs, proteins and molecular clusters, and direct information about these processes can be obtained from tunneling splittings. Carboxylic acid dimers are prototypes for multiple proton transfer, of which the formic acid dimer is the simplest one. Here, we present efficient quantum dynamics calculations of ground-state and fundamental excitation tunneling splittings in the formic acid dimer and its deuterium isotopologues. These are achieved with a multidimensional scheme developed by us, in which the saddle-point normal coordinates are chosen, the basis functions are customized for the proton transfer process, and the preconditioned inexact spectral transform method is used to solve the resultant eigenvalue problem. Our computational results are in excellent agreement with the most recent experiments (Zhang et al., 2017; Li et al., 2019).

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“…The limiting case of a symmetric-top rotor is methodologically important, even for an asymmetric-top rotor treated exactly without any approximations, since it is always useful to split the terms in Eqs. (8) and (10) such that ̂r ot =̂s ym +̂a sym…”

Section: B the Limits Of Prolate And Oblate Symmetric Topsmentioning

confidence: 99%

“…With rotation–vibration interaction terms included, the size of the Hamiltonian matrix is usually huge, and the numerical cost of its diagonalization is very significant, often unpractical. In the literature, such nearly exact calculations of the rotational–vibrational spectra have been reported for H 3 + , HeHF, LiNC, HeN 2 + , H 2 O, H 2 S, SO 2 , , HO 2 , Ar 3 , and very recently for O 3 . For an accurate ro-vibrational spectrum like that, even after it has already been computed, the process of assigning the vibration mode quantum numbers ( v 1 , v 2 , v 3 ) and the asymmetric-top rotor quantum numbers ( J KaKc ) to the individual rotational–vibrational states is also challenging …”

Section: Introductionmentioning

confidence: 99%

Theoretical Treatment of the Coriolis Effect Using Hyperspherical Coordinates, with Application to the Ro-Vibrational Spectrum of Ozone

et al. 2020

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Several alternative methods for description of interaction between rotation and vibration are compared and contrasted using hyper-spherical coordinates for a triatomic molecule. These methods differ by the choice of z-axis and by the assumption of a prolate or oblate rotor shape of the molecule. For each case, block-structure of the rotational-vibrational Hamiltonian matrix is derived and analyzed, and the advantages and disadvantages of each method are made explicit.This theory is then employed to compute ro-vibrational spectra of singly substituted ozone; roughly, 600 vibrational states of 16 O 18 O 16 O and 16 O 16 O 18 O isomers combined, with rotational excitations up to = 5 and both inversion parities (21600 coupled ro-vibrational states total). Splittings between the states of different parities, so called K-doublings, are calculated and analyzed. The roles of the asymmetric-top rotor term and the Coriolis coupling term are determined individually, and it is found that they both affect these splittings, but in the opposite directions. Thus, the two effects partially cancel out, and the residual splittings are relatively small. Energies of the ro-vibrational states reported in this work for 16 O 18 O 16 O and 16 O 16 O 18 O are in excellent agreement with literature (available for low vibrational excitation). New data obtained here for the highly excited vibrational states enable the first systematic study of the Coriolis effect in symmetric and asymmetric isotopomers of ozone.

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Accurate calculations of bound rovibrational states for argon trimer

Cited by 13 publications

References 62 publications

Efficient Quantum Mechanical Calculations of Mode-Specific Tunneling Splittings upon Fundamental Excitation in the Dimer of Formic Acid

Efficient Quantum Mechanical Calculations of Mode-Specific Tunneling Splittings upon Fundamental Excitation in the Dimer of Formic Acid

Double Proton Transfer in the Dimer of Formic Acid: An Efficient Quantum Mechanical Scheme

Theoretical Treatment of the Coriolis Effect Using Hyperspherical Coordinates, with Application to the Ro-Vibrational Spectrum of Ozone

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