Temperature-dependent, effective structures of the 14NH 3 and 14ND 3 molecules

István Szabó, Csaba Fábri, Gábor Czakó, Edit Mátyus, Attila G. Császár

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Measurements result in effective, usually temperature-dependent structural parameters of molecules, and never directly in equilibrium structures, which are theoretical constructs. A recent high-accuracy semiglobal potential energy surface of the electronic ground state of the ammonia molecule, called NH3-Y2010 (J. Mol. Spectrosc.2011, 268, 123), which exhibits mass-independent equilibrium NH bond length and a HNH bond angle of 1.0109 Å and 106.75°, respectively, is employed together with the variational nuclear motion code GENIUSH (J. Chem. Phys. 2009, 130, 134112; 2011, 134, 074105) to determine directly measurable, effective structural parameters of the 14NH 3 and 14ND 3 molecules. The effective r g- and r a-type NH(ND) distances determined at 300 K are 1.0307(1.0254) and 1.0256(1.0217) Å, respectively, with an estimated accuracy of 2 × 10 -4 Å. The effective g HNH and DND bond angles at 300 K are 106.91° and 106.85°, respectively. The root-mean-square amplitudes of vibration, l g, for the NH(ND) distances at 300 K are 0.073(0.062) Å. These structural parameters confirm the less accurate results of a room-temperature gas-electron-diffraction study (J. Chem. Phys. 1968, 49, 2488, all data in Å): r g(NH) = 1.030(2), l g(NH) = 0.073(2), r g(ND) = 1.027(3), and l g(ND) = 0.061(2). The computed difference in the r g,T(NH) bond lengths of the two spin isomers (ortho and para forms) of 14NH 3 is 3 × 10 -5 Å at 0 K, the difference diminishes at temperatures of about 30-50 K.

Original languageEnglish
Pages (from-to)4356-4362
Number of pages7
JournalJournal of Physical Chemistry A
Volume116
Issue number17
DOIs
Publication statusPublished - May 3 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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