TY - JOUR

T1 - Isomeric interconversion in the linear Cl−-HD anion complex

AU - Wilson, R.L.

AU - Loh, Z.M.

AU - Wild, Duncan

AU - Bieske, E.J.

AU - Buchachenko, A.A.

PY - 2004

Y1 - 2004

N2 - The rotationally resolved infrared photodissociation spectrum of Cl−-HD is measured in the HD stretch region. Two Σ-Σ bands are observed, corresponding to transitions from the ground state [the (vHD = 0, n = 0) level] and first excited intermolecular bend state [the (vHD = 0, n = 1) level]. The (vHD = 0, n = 0) and (vHD = 0, n = 1) states are predominantly associated with the linear Cl−⋯DH and Cl−⋯HD geometries, respectively. The spectrum is complicated by perturbative interactions between levels of the (vHD = 0, n = 0) and (vHD = 0, n = 1) rotational manifolds and between levels of the (vHD = 1, n = 0) and (vHD = 1, n = 1) rotational manifolds. A global fit to the transition frequencies, taking the lower and upper state perturbations into account, yields zero-order rotational and centrifugal distortion constants and allows us to establish that the (vHD = 0, n = 1, J″ = 0) level lies 13.7 cm−1 above the (vHD = 0, n = 0, J″ = 0) level. Rovibrational energy level calculations performed using a recent ab initio potential energy surface confirm the picture emerging from the experimental data and provide good agreement with measured molecular parameters. The results emphasize the importance of quantum mechanical interconversion between two isomeric structures of a simple anion complex. © 2004 American Institute of Physics.

AB - The rotationally resolved infrared photodissociation spectrum of Cl−-HD is measured in the HD stretch region. Two Σ-Σ bands are observed, corresponding to transitions from the ground state [the (vHD = 0, n = 0) level] and first excited intermolecular bend state [the (vHD = 0, n = 1) level]. The (vHD = 0, n = 0) and (vHD = 0, n = 1) states are predominantly associated with the linear Cl−⋯DH and Cl−⋯HD geometries, respectively. The spectrum is complicated by perturbative interactions between levels of the (vHD = 0, n = 0) and (vHD = 0, n = 1) rotational manifolds and between levels of the (vHD = 1, n = 0) and (vHD = 1, n = 1) rotational manifolds. A global fit to the transition frequencies, taking the lower and upper state perturbations into account, yields zero-order rotational and centrifugal distortion constants and allows us to establish that the (vHD = 0, n = 1, J″ = 0) level lies 13.7 cm−1 above the (vHD = 0, n = 0, J″ = 0) level. Rovibrational energy level calculations performed using a recent ab initio potential energy surface confirm the picture emerging from the experimental data and provide good agreement with measured molecular parameters. The results emphasize the importance of quantum mechanical interconversion between two isomeric structures of a simple anion complex. © 2004 American Institute of Physics.

U2 - 10.1063/1.1763569

DO - 10.1063/1.1763569

M3 - Article

VL - 121

SP - 2085

EP - 2093

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 5

ER -