TY - JOUR

T1 - Quantum dynamical calculation of bound rovibrational states of HO 2 up to largest possible total angular momentum, J ≤ 130

AU - Petty, Corey

AU - Chen, Wenwu

AU - Poirier, Bill

N1 - Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.

PY - 2013/8/15

Y1 - 2013/8/15

N2 - In a previous article [J. Theor. Comput. Chem. 2010, 9, 435], all rovibrational bound states of HO2 were systematically computed, for all total angular momentum values J = 0-10. In this article, the high-J rovibrational states are computed for every multiple-of-ten J value up to J = 130, which is the point where the centrifugal barrier obliterates the potential well, and bound states no longer exist. The results are used to assess the importance of Coriolis coupling in this floppy system and to evaluate two different J-shifting schemes. Though not effective for multiply vibrationally excited bound states, vibrational-state-dependent J-shifting obtains modestly accurate predictions for the lowest-lying energies [J. Phys. Chem. A 2006, 110, 3246]. However, much better performance is obtained - especially for large J values, and despite substantial Coriolis coupling - using a second, rotational-state-dependent J-shifting scheme [J. Chem. Phys. 1998, 108, 5216], for which the rotational constants themselves depend on J and K. The latter formalism also yields important dynamical insight into the structure of the strongly Coriolis-coupled eigenstate wave functions. The calculations were performed using ScalIT, a suite of codes enabling quantum dynamics calculations on massively parallel computing architectures.

AB - In a previous article [J. Theor. Comput. Chem. 2010, 9, 435], all rovibrational bound states of HO2 were systematically computed, for all total angular momentum values J = 0-10. In this article, the high-J rovibrational states are computed for every multiple-of-ten J value up to J = 130, which is the point where the centrifugal barrier obliterates the potential well, and bound states no longer exist. The results are used to assess the importance of Coriolis coupling in this floppy system and to evaluate two different J-shifting schemes. Though not effective for multiply vibrationally excited bound states, vibrational-state-dependent J-shifting obtains modestly accurate predictions for the lowest-lying energies [J. Phys. Chem. A 2006, 110, 3246]. However, much better performance is obtained - especially for large J values, and despite substantial Coriolis coupling - using a second, rotational-state-dependent J-shifting scheme [J. Chem. Phys. 1998, 108, 5216], for which the rotational constants themselves depend on J and K. The latter formalism also yields important dynamical insight into the structure of the strongly Coriolis-coupled eigenstate wave functions. The calculations were performed using ScalIT, a suite of codes enabling quantum dynamics calculations on massively parallel computing architectures.

UR - http://www.scopus.com/inward/record.url?scp=84882396393&partnerID=8YFLogxK

U2 - 10.1021/jp401154m

DO - 10.1021/jp401154m

M3 - Article

C2 - 23700970

AN - SCOPUS:84882396393

VL - 117

SP - 7280

EP - 7297

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 32

ER -