Spectroscopic Study of the Br^- +CH₃ I→I^- +CH₃ Br S_N 2 Reaction.

Mass spectrometry and anion photoelectron spectroscopy have been used to study the gas-phase <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msub><mml:mi>S</mml:mi> <mml:mi>N</mml:mi></mml:msub> <mml:mn>2</mml:mn></mml:mrow> <mml:annotation>${{{\rm S}}_{{\rm N}}2}$</mml:annotation> </mml:semantics> </mml:math> reaction involving <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:msup><mml:mrow><mml:mi>B</mml:mi> <mml:mi>r</mml:mi></mml:mrow> <mml:mo>-</mml:mo></mml:msup> <mml:annotation>${{{\rm B}{\rm r}}^{-}}$</mml:annotation> </mml:semantics> </mml:math> and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow> <mml:msub><mml:mrow><mml:mi>C</mml:mi> <mml:mi>H</mml:mi></mml:mrow> <mml:mn>3</mml:mn></mml:msub> <mml:mi>I</mml:mi></mml:mrow> <mml:annotation>${{{\rm C}{\rm H}}_{3}{\rm I}}$</mml:annotation> </mml:semantics> </mml:math> . The anion photoelectron spectra associated with the reaction intermediates of this <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msub><mml:mi>S</mml:mi> <mml:mi>N</mml:mi></mml:msub> <mml:mn>2</mml:mn></mml:mrow> <mml:annotation>${{{\rm S}}_{{\rm N}}2}$</mml:annotation> </mml:semantics> </mml:math> reaction are presented. High-level CCSD(T) calculations have been utilised to investigate the reaction intermediates that may form as a result of the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:semantics> <mml:mrow><mml:msub><mml:mi>S</mml:mi> <mml:mi>N</mml:mi></mml:msub> <mml:mn>2</mml:mn></mml:mrow> <mml:annotation>${{{\rm S}}_{{\rm N}}2}$</mml:annotation> </mml:semantics> </mml:math> reaction along various different reaction pathways, including back-side attack and front-side attack. In addition, simulated vertical detachment energies of each reaction intermediate have been calculated to rationalise the photoelectron spectra.