Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

Mátyus, Edit; Szidarovszky, Tamás

doi:10.1063/1.4897566

Title: Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

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Abstract

Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H{sub 3}{sup +}, for which a global adiabatic potential energy surface accurate to better than 0.1 cm{sup −1} exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D{sub 3h} point-group symmetry is employed. The vibrational mass of the proton in H{sub 3}{sup +} is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m{sub opt,p}{sup (v)}=m{sub nuc,p}+0.31224 m{sub e}. This optimized vibrational mass, along with a nuclear rotational mass, reducesmore »« less

Authors:

Mátyus, Edit ^[1]; Szidarovszky, Tamás ^[2]

Institute of Chemistry, Eötvös University, P.O. Box 32, H-1518 Budapest 112 (Hungary)
MTA-ELTE Research Group on Complex Chemical Systems, Pázmány Péter sétány 1/A, H-1117 Budapest (Hungary)

Publication Date:: Tue Oct 21 00:00:00 EDT 2014

OSTI Identifier:: 22436599

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 141; Journal Issue: 15; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; ELECTRONS; ENERGY LEVELS; HAMILTONIANS; HYDROGEN IONS 3 PLUS; MASS; MOLECULES; POTENTIAL ENERGY; PROTONS; SCHROEDINGER EQUATION; SIMULATION

Citation Formats


                    Mátyus, Edit, Szidarovszky, Tamás, and Császár, Attila G., E-mail: csaszar@chem.elte.hu. Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces.  United States: N. p., 2014. 
        Web.  doi:10.1063/1.4897566.

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                    Mátyus, Edit, Szidarovszky, Tamás, & Császár, Attila G., E-mail: csaszar@chem.elte.hu. Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces.  United States.  https://doi.org/10.1063/1.4897566

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                    Mátyus, Edit, Szidarovszky, Tamás, and Császár, Attila G., E-mail: csaszar@chem.elte.hu. 2014.  
        "Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces".  United States.  https://doi.org/10.1063/1.4897566.

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@article{osti_22436599,

  title        = {Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces},

  author       = {Mátyus, Edit and Szidarovszky, Tamás and Császár, Attila G., E-mail: csaszar@chem.elte.hu},

  abstractNote = {Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H{sub 3}{sup +}, for which a global adiabatic potential energy surface accurate to better than 0.1 cm{sup −1} exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D{sub 3h} point-group symmetry is employed. The vibrational mass of the proton in H{sub 3}{sup +} is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m{sub opt,p}{sup (v)}=m{sub nuc,p}+0.31224 m{sub e}. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.},

  doi          = {10.1063/1.4897566},

  url          = {https://www.osti.gov/biblio/22436599},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 15,

  volume       = 141,

  place        = {United States},

  year         = {Tue Oct 21 00:00:00 EDT 2014},

  month        = {Tue Oct 21 00:00:00 EDT 2014}

}

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