Franck-Condon simulation of the single-vibronic-level emission spectra of HPCI/DPCl and the chemiluminescence spectrum of HPCI, including anharmonicity

Restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] potential energy functions (PEFs) were calculated for the (X) over tilde (2)A" and (A) over tilde (2)A' states of HPCl employing the augmented correlation-consistent polarized-valence-quadruple-zeta (aug-cc-pVQZ) basis set. Further geometry optimization calculations were carried out on both electronic states of HPCl at the RCCSD(T) level with all electron and quasirelativistic effective core potential basis sets of better than the aug-cc-pVQZ quality, and also including some core electrons, in order to obtain more reliable geometrical parameters and relative electronic energy of the two states. Anharmonic vibrational wave functions of the two states of HPCl and DPCl, and Franck-Condon (FC) factors of the (A) over tilde (2)A'-(X) over tilde (2)A" transition were computed employing the RCCSD(T)/aug-cc-pVQZ PEFs. Calculated FC factors with allowance for Duschinsky rotation and anharmonicity were used to simulate the single-vibronic-level (SVL) emission spectra of HPCl and DPCl reported by Brandon et al. [J. Chem. Phys. 119, 2037 (2003)] and the chemiluminescence spectrum reported by Bramwell et al. [Chem. Phys. Lett. 331, 483 (2000)]. Comparison between simulated and observed SVL emission spectra gives the experimentally derived equilibrium geometry of the (A) over tilde (2)A' state of HPCl of r(e)(PCI)=2.0035 +/- 0.0015 Angstrom, theta(e) = 116.08 +/- 0.60degrees, and r(e)(HP) = 1.4063 +/- 0.0015 Angstrom via the iterative Franck-Condon analysis procedure. Comparison between simulated and observed chemiluminescence spectra confirms that the vibrational population distribution of the (A) over tilde (2)A' state-of HPCl is non-Boltzmann, as proposed by Baraille, et al. [Chem. Phy. 289, 263 (2003)]. (C) 2004 American Institute of Physics.