Equilibrium structure and torsional barrier of BH3NH3

Jean Demaison, Jacques Liévin, A. Császár, Claudine Gutle

Research output: Contribution to journalArticle

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Abstract

Born-Oppenheimer equilibrium structures, re BO, of the electronic ground state of the borazane (BH3NH3) molecule of C3v., point-group symmetry are computed ab initio using the CCSD(T) method with basis sets up to quintuple-ζ quality. Inclusion of the counterpoise correction and extrapolation of the structural parameters to the complete basis set limit yield a best estimate of re BO of BH3NH3. The anharmonic force field of BH 3NH3, computed at the CCSD(T) level of theory with a basis set of triple-ζ quality, allows the determination of semi-experimental equilibrium rotational constants, which in turn result in a semi-experimental equilibrium structure, re SE. The re BO and re SE structures are in excellent agreement, indicating the validity of the methods used for their determination. The empirical mass-dependent structure, rm (1), of BH 3NH3 is also determined. Although it is inferior in quality to the previous two structures, it is much more accurate than the standard empirical r0 and rs structures reported earlier for BH3NH3. The semi-experimental re SE as well as the empirical rm (1) structures determined are based on experimental ground-state rotational constants available from the literature for nine isotopologues of borazane. The effective barrier to the internal rotation of BH3NH3, a molecule isoelectronic with CH3CH3, has been computed ab initio, employing the focal-point analysis (FPA) approach, to be 699 ±11 cm -1. This compares favorably with an empirical redetermination of the effective barrier based on the above re SE structure, V3 = 718(17) cm-1.

Original languageEnglish
Pages (from-to)4477-4482
Number of pages6
JournalJournal of Physical Chemistry A
Volume112
Issue number19
DOIs
Publication statusPublished - May 15 2008

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Ground state
Point groups
Molecules
Crystal symmetry
Extrapolation
ground state
field theory (physics)
extrapolation
molecules
inclusions
symmetry
estimates
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Equilibrium structure and torsional barrier of BH3NH3 . / Demaison, Jean; Liévin, Jacques; Császár, A.; Gutle, Claudine.

In: Journal of Physical Chemistry A, Vol. 112, No. 19, 15.05.2008, p. 4477-4482.

Research output: Contribution to journalArticle

Demaison, Jean ; Liévin, Jacques ; Császár, A. ; Gutle, Claudine. / Equilibrium structure and torsional barrier of BH3NH3 In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 19. pp. 4477-4482.
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