Surprising Quenching of the Spin-Orbit Interaction Significantly Diminishes H2O⋯X [X = F, Cl, Br, I] Dissociation Energies

G. Czakó, A. Császár, Henry F. Schaefer

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The H2O⋯X complexes, with X = F, Cl, Br, and I, show considerable viability with nonspin-orbit De(D0) dissociation energy values of 3.73(2.42), 3.60(2.68), 3.54(2.72), and 3.36(2.77) kcal mol-1 for X = F, Cl, Br, and I, respectively, obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using relativistic pseudopotentials (PPs) for Br and I. Spin-orbit (SO) corrections, computed with the Breit-Pauli operator in the interacting states approach at the all-electron MRCI+Q/aug-cc-pwCVTZ(-PP) level, are found to depend sensitively and unpredictably on the O⋯X separations. 96% (F), 87% (Cl), 54% (Br), and 30% (I) quenching of the SO corrections significantly reduces the dissociation energies of the H2O⋯X complexes, resulting in De(D0) values of 3.38(2.06), 2.86(1.94), 1.64(0.83), and 1.23(0.64) kcal mol-1 for X = F, Cl, Br, and I, respectively. (Graph Presented).

Original languageEnglish
Pages (from-to)11956-11961
Number of pages6
JournalJournal of Physical Chemistry A
Volume118
Issue number51
DOIs
Publication statusPublished - Dec 26 2014

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spin-orbit interactions
pseudopotentials
Quenching
Orbits
quenching
dissociation
orbits
relativistic theory
viability
energy
operators
Electrons
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Surprising Quenching of the Spin-Orbit Interaction Significantly Diminishes H2O⋯X [X = F, Cl, Br, I] Dissociation Energies. / Czakó, G.; Császár, A.; Schaefer, Henry F.

In: Journal of Physical Chemistry A, Vol. 118, No. 51, 26.12.2014, p. 11956-11961.

Research output: Contribution to journalArticle

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abstract = "The H2O⋯X complexes, with X = F, Cl, Br, and I, show considerable viability with nonspin-orbit De(D0) dissociation energy values of 3.73(2.42), 3.60(2.68), 3.54(2.72), and 3.36(2.77) kcal mol-1 for X = F, Cl, Br, and I, respectively, obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using relativistic pseudopotentials (PPs) for Br and I. Spin-orbit (SO) corrections, computed with the Breit-Pauli operator in the interacting states approach at the all-electron MRCI+Q/aug-cc-pwCVTZ(-PP) level, are found to depend sensitively and unpredictably on the O⋯X separations. 96{\%} (F), 87{\%} (Cl), 54{\%} (Br), and 30{\%} (I) quenching of the SO corrections significantly reduces the dissociation energies of the H2O⋯X complexes, resulting in De(D0) values of 3.38(2.06), 2.86(1.94), 1.64(0.83), and 1.23(0.64) kcal mol-1 for X = F, Cl, Br, and I, respectively. (Graph Presented).",
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AB - The H2O⋯X complexes, with X = F, Cl, Br, and I, show considerable viability with nonspin-orbit De(D0) dissociation energy values of 3.73(2.42), 3.60(2.68), 3.54(2.72), and 3.36(2.77) kcal mol-1 for X = F, Cl, Br, and I, respectively, obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using relativistic pseudopotentials (PPs) for Br and I. Spin-orbit (SO) corrections, computed with the Breit-Pauli operator in the interacting states approach at the all-electron MRCI+Q/aug-cc-pwCVTZ(-PP) level, are found to depend sensitively and unpredictably on the O⋯X separations. 96% (F), 87% (Cl), 54% (Br), and 30% (I) quenching of the SO corrections significantly reduces the dissociation energies of the H2O⋯X complexes, resulting in De(D0) values of 3.38(2.06), 2.86(1.94), 1.64(0.83), and 1.23(0.64) kcal mol-1 for X = F, Cl, Br, and I, respectively. (Graph Presented).

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