Opposite Effects of the Rotational and Translational Energy on the Rates of Ion-Molecule Reactions near 0 K: The D2++NH3 and <mml:math xmlns:mml="http://www.w3…

The ion-molecule reactions <a:math xmlns:a="http://www.w3.org/1998/Math/MathML" display="inline"><a:msubsup><a:mi mathvariant="normal">D</a:mi><a:mn>2</a:mn><a:mo>+</a:mo></a:msubsup><a:mo>+</a:mo><a:msub><a:mrow><a:mi>NH</a:mi></a:mrow><a:mn>3</a:mn></a:msub></a:math> and <d:math xmlns:d="http://www.w3.org/1998/Math/MathML" display="inline"><d:msubsup><d:mi mathvariant="normal">D</d:mi><d:mn>2</d:mn><d:mo>+</d:mo></d:msubsup><d:mo>+</d:mo><d:msub><d:mrow><d:mi>ND</d:mi></d:mrow><d:mn>3</d:mn></d:msub></d:math> are studied at low collision energies (<g:math xmlns:g="http://www.w3.org/1998/Math/MathML" display="inline"><g:msub><g:mi>E</g:mi><g:mrow><g:mi>coll</g:mi></g:mrow></g:msub></g:math> from zero to approximately <i:math xmlns:i="http://www.w3.org/1998/Math/MathML" display="inline"><i:msub><i:mi>k</i:mi><i:mi>B</i:mi></i:msub><i:mo>×</i:mo><i:mn>50</i:mn><i:mtext> </i:mtext><i:mtext> </i:mtext><i:mi mathvariant="normal">K</i:mi></i:math>), with the <l:math xmlns:l="http://www.w3.org/1998/Math/MathML" display="inline"><l:mrow><l:msubsup><l:mrow><l:mi mathvariant="normal">D</l:mi></l:mrow><l:mrow><l:mn>2</l:mn></l:mrow><l:mrow><l:mo>+</l:mo></l:mrow></l:msubsup></l:mrow></l:math> ions in the ground rovibrational state and for different rotational temperatures of the ammonia molecules, using the Rydberg-Stark merged-beam approach. Two different rotational temperatures (approximately 15 K and approximately 40 K), measured by (<o:math xmlns:o="http://www.w3.org/1998/Math/MathML" display="inline"><o:mrow><o:mn>2</o:mn><o:mo>+</o:mo><o:mn>1</o:mn></o:mrow></o:math>) resonance-enhanced multiphoton-ionization spectroscopy, are obtained by using a seeded supersonic expansion in He and a pure ammonia expansion, respectively. The experimental data reveal a strong enhancement of the rate coefficients at the lowest collision energies caused by the charge-dipole interaction. Calculations based on a rotationally adiabatic capture model accurately reproduce the observed kinetic-energy dependence of the rate coefficients. The rate coefficients increase with increasing rotational temperature of the ammonia molecules, which contradicts the expectation that rotational excitation should average the dipoles out. Moreover, these reactions exhibit a pronounced inverse kinetic isotope effect. The difference is caused by nuclear-spin-statistical factors and the smaller rotational constants and tunneling splittings in <q:math xmlns:q="http://www.w3.org/1998/Math/MathML" display="inline"><q:mrow><q:msub><q:mrow><q:mi>ND</q:mi></q:mrow><q:mrow><q:mn>3</q:mn></q:mrow></q:msub></q:mrow></q:math>. Published by the American Physical Society 2024