<p>In this work, we studied the helium-induced collisional excitation of the radical ion HCl<sup>+</sup>. Our work focuses on calculating two-dimensional potential energy surfaces (PES) to study the interaction due to the collision between HCl<sup>+</sup> and He, and on analyzing the influence of the isotopic effect on cross sections and collision rates. For <i>Ab initio</i> calculations of PES <InlineEquation ID="IEq3"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10509_2025_4484_Article_IEq3.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="26" /> </InlineMediaObject> <EquationSource Format="MATHML"><math> <mmultiscripts> <mi>A</mi> <none /> <mo>′</mo> <mprescripts /> <none /> <mn>2</mn> </mmultiscripts> </math></EquationSource> <EquationSource Format="TEX">$^{2}A^{\prime }$</EquationSource> </InlineEquation> and <InlineEquation ID="IEq4"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10509_2025_4484_Article_IEq4.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="29" /> </InlineMediaObject> <EquationSource Format="MATHML"><math> <mmultiscripts> <mi>A</mi> <none /> <mo>′′</mo> <mprescripts /> <none /> <mn>2</mn> </mmultiscripts> </math></EquationSource> <EquationSource Format="TEX">$^{2}A^{\prime \prime }$</EquationSource> </InlineEquation> of HCl<sup>+</sup>(X<InlineEquation ID="IEq5"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10509_2025_4484_Article_IEq5.gif" Format="GIF" Height="16" Rendition="HTML" Resolution="72" Type="Linedraw" Width="20" /> </InlineMediaObject> <EquationSource Format="MATHML"><math> <mmultiscripts> <mi mathvariant="normal">Π</mi> <mprescripts /> <none /> <mn>2</mn> </mmultiscripts> </math></EquationSource> <EquationSource Format="TEX">$^{2}\Pi $</EquationSource> </InlineEquation>)-He complex, we used the RCCSD(T)-F12 method with cc-pVQZ-F12 basis sets. These surfaces have been fitted using the Reproducing Kernel Hilbert Space (RKHS) method and were submitted to the close-coupling approach in order to work out the inelastic integral cross sections. Collision cross sections taking into account the fine structures of HCl<sup>+</sup> have been performed for kinetic energies up to 3500 cm<sup>−1</sup> and the thermal excitation rates for kinetic temperatures varying from <InlineEquation ID="IEq6"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="10509_2025_4484_Article_IEq6.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="27" /> </InlineMediaObject> <EquationSource Format="MATHML"><math> <mn>4</mn> <mi>K</mi> </math></EquationSource> <EquationSource Format="TEX">$4K$</EquationSource> </InlineEquation> up to 400 K. It appears that the difference in the cross section and collisional rate cofficients for the H<sup>35</sup>Cl<sup>+</sup> and H<sup>37</sup>Cl<sup>+</sup> colliding with He was found to be negligeable. In contrast, a significant difference in effective cross-sections and collision rates between HCl<sup>+</sup>-He and DCl<sup>+</sup>-He was observed to the extent that it is impossible to make estimation of collision rates of deuterated species from those of the hydrogenated species.</p>

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Effective cross sections and rates coefficients derived from collision-induced rotational excitation of HCl\(^{+}(X^{2}\Pi )\) with He(\(^{1}S\)): isotopic effects

  • Joseph Ngueleo Baldagui,
  • Théophile Tchakoua,
  • Jean Jules Fifen,
  • Mama Nsangou

摘要

In this work, we studied the helium-induced collisional excitation of the radical ion HCl+. Our work focuses on calculating two-dimensional potential energy surfaces (PES) to study the interaction due to the collision between HCl+ and He, and on analyzing the influence of the isotopic effect on cross sections and collision rates. For Ab initio calculations of PES A 2 $^{2}A^{\prime }$ and A ′′ 2 $^{2}A^{\prime \prime }$ of HCl+(X Π 2 $^{2}\Pi $ )-He complex, we used the RCCSD(T)-F12 method with cc-pVQZ-F12 basis sets. These surfaces have been fitted using the Reproducing Kernel Hilbert Space (RKHS) method and were submitted to the close-coupling approach in order to work out the inelastic integral cross sections. Collision cross sections taking into account the fine structures of HCl+ have been performed for kinetic energies up to 3500 cm−1 and the thermal excitation rates for kinetic temperatures varying from 4 K $4K$ up to 400 K. It appears that the difference in the cross section and collisional rate cofficients for the H35Cl+ and H37Cl+ colliding with He was found to be negligeable. In contrast, a significant difference in effective cross-sections and collision rates between HCl+-He and DCl+-He was observed to the extent that it is impossible to make estimation of collision rates of deuterated species from those of the hydrogenated species.