Two-electron relativistic corrections to the potential energy surface and vibration-rotation levels of water

Harry M. Quiney, Paolo Barletta, G. Tarczay, A. Császár, Oleg L. Polyansky, Jonathan Tennyson

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Two-electron relativistic corrections to the ground-state electronic energy of water are determined as a function of geometry at over 300 points. The corrections include the two-electron Darwin term (D2) of the Coulomb-Pauli Hamiltonian, obtained at the cc-pVQZ CCSD(T) level of theory, as well as the Gaunt and Breit corrections, calculated perturbationally using four-component fully variational Dirac-Hartree-Fock (DHF) wavefunctions and two different basis sets. Based on the calculated energy points, fitted relativistic correction surfaces are constructed. These surfaces are used with a high-accuracy ab initio nonrelativistic Born-Oppenheimer (BO) potential energy hypersurface to calculate vibrational band origins and rotational term values for H216O. The calculations suggest that these two-electron relativistic corrections, which go beyond the usual kinetic relativistic effects and which have so far been neglected in rovibrational calculations on light many-electron molecular systems, have a substantial influence on the rotation-vibration levels of water. The three effects considered have markedly different characteristics for the stretching and bending levels, which often leads to fortuitous cancellation of errors. The effect of the Breit interaction on the rovibrational levels is intermediate between the effect of the kinetic relativistic correction and that of the one-electron Lamb-shift effect.

Original languageEnglish
Pages (from-to)413-420
Number of pages8
JournalChemical Physics Letters
Volume344
Issue number3-4
DOIs
Publication statusPublished - Aug 24 2001

Fingerprint

Potential energy surfaces
potential energy
vibration
Electrons
Water
water
electrons
Hamiltonians
Kinetics
Wave functions
Potential energy
Ground state
kinetics
Stretching
relativistic effects
cancellation
Geometry
ground state
energy
shift

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Two-electron relativistic corrections to the potential energy surface and vibration-rotation levels of water. / Quiney, Harry M.; Barletta, Paolo; Tarczay, G.; Császár, A.; Polyansky, Oleg L.; Tennyson, Jonathan.

In: Chemical Physics Letters, Vol. 344, No. 3-4, 24.08.2001, p. 413-420.

Research output: Contribution to journalArticle

Quiney, Harry M. ; Barletta, Paolo ; Tarczay, G. ; Császár, A. ; Polyansky, Oleg L. ; Tennyson, Jonathan. / Two-electron relativistic corrections to the potential energy surface and vibration-rotation levels of water. In: Chemical Physics Letters. 2001 ; Vol. 344, No. 3-4. pp. 413-420.
@article{7e0f6e2e3f3a4abc958a86d05d5d95f4,
title = "Two-electron relativistic corrections to the potential energy surface and vibration-rotation levels of water",
abstract = "Two-electron relativistic corrections to the ground-state electronic energy of water are determined as a function of geometry at over 300 points. The corrections include the two-electron Darwin term (D2) of the Coulomb-Pauli Hamiltonian, obtained at the cc-pVQZ CCSD(T) level of theory, as well as the Gaunt and Breit corrections, calculated perturbationally using four-component fully variational Dirac-Hartree-Fock (DHF) wavefunctions and two different basis sets. Based on the calculated energy points, fitted relativistic correction surfaces are constructed. These surfaces are used with a high-accuracy ab initio nonrelativistic Born-Oppenheimer (BO) potential energy hypersurface to calculate vibrational band origins and rotational term values for H216O. The calculations suggest that these two-electron relativistic corrections, which go beyond the usual kinetic relativistic effects and which have so far been neglected in rovibrational calculations on light many-electron molecular systems, have a substantial influence on the rotation-vibration levels of water. The three effects considered have markedly different characteristics for the stretching and bending levels, which often leads to fortuitous cancellation of errors. The effect of the Breit interaction on the rovibrational levels is intermediate between the effect of the kinetic relativistic correction and that of the one-electron Lamb-shift effect.",
author = "Quiney, {Harry M.} and Paolo Barletta and G. Tarczay and A. Cs{\'a}sz{\'a}r and Polyansky, {Oleg L.} and Jonathan Tennyson",
year = "2001",
month = "8",
day = "24",
doi = "10.1016/S0009-2614(01)00784-9",
language = "English",
volume = "344",
pages = "413--420",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "3-4",

}

TY - JOUR

T1 - Two-electron relativistic corrections to the potential energy surface and vibration-rotation levels of water

AU - Quiney, Harry M.

AU - Barletta, Paolo

AU - Tarczay, G.

AU - Császár, A.

AU - Polyansky, Oleg L.

AU - Tennyson, Jonathan

PY - 2001/8/24

Y1 - 2001/8/24

N2 - Two-electron relativistic corrections to the ground-state electronic energy of water are determined as a function of geometry at over 300 points. The corrections include the two-electron Darwin term (D2) of the Coulomb-Pauli Hamiltonian, obtained at the cc-pVQZ CCSD(T) level of theory, as well as the Gaunt and Breit corrections, calculated perturbationally using four-component fully variational Dirac-Hartree-Fock (DHF) wavefunctions and two different basis sets. Based on the calculated energy points, fitted relativistic correction surfaces are constructed. These surfaces are used with a high-accuracy ab initio nonrelativistic Born-Oppenheimer (BO) potential energy hypersurface to calculate vibrational band origins and rotational term values for H216O. The calculations suggest that these two-electron relativistic corrections, which go beyond the usual kinetic relativistic effects and which have so far been neglected in rovibrational calculations on light many-electron molecular systems, have a substantial influence on the rotation-vibration levels of water. The three effects considered have markedly different characteristics for the stretching and bending levels, which often leads to fortuitous cancellation of errors. The effect of the Breit interaction on the rovibrational levels is intermediate between the effect of the kinetic relativistic correction and that of the one-electron Lamb-shift effect.

AB - Two-electron relativistic corrections to the ground-state electronic energy of water are determined as a function of geometry at over 300 points. The corrections include the two-electron Darwin term (D2) of the Coulomb-Pauli Hamiltonian, obtained at the cc-pVQZ CCSD(T) level of theory, as well as the Gaunt and Breit corrections, calculated perturbationally using four-component fully variational Dirac-Hartree-Fock (DHF) wavefunctions and two different basis sets. Based on the calculated energy points, fitted relativistic correction surfaces are constructed. These surfaces are used with a high-accuracy ab initio nonrelativistic Born-Oppenheimer (BO) potential energy hypersurface to calculate vibrational band origins and rotational term values for H216O. The calculations suggest that these two-electron relativistic corrections, which go beyond the usual kinetic relativistic effects and which have so far been neglected in rovibrational calculations on light many-electron molecular systems, have a substantial influence on the rotation-vibration levels of water. The three effects considered have markedly different characteristics for the stretching and bending levels, which often leads to fortuitous cancellation of errors. The effect of the Breit interaction on the rovibrational levels is intermediate between the effect of the kinetic relativistic correction and that of the one-electron Lamb-shift effect.

UR - http://www.scopus.com/inward/record.url?scp=0000092718&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000092718&partnerID=8YFLogxK

U2 - 10.1016/S0009-2614(01)00784-9

DO - 10.1016/S0009-2614(01)00784-9

M3 - Article

AN - SCOPUS:0000092718

VL - 344

SP - 413

EP - 420

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 3-4

ER -