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

By Foo-tim Chau, Daniel K.W. Mok, Edmond P.F. Lee and John M. Dyke


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)]

Topics: TP, QD
Year: 2004
OAI identifier: oai:eprints.soton.ac.uk:20166
Provided by: e-Prints Soton

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  1. 115, 7348 ~2001!; Hermann Stoll ~stoll@theochem.uni-stuttgart.de! or Michael Dolg ~dolg@thch.unibonn.de or m.dolg@uni-koeln.de! 17MOLPRO is a package of ab initio programs written by H.-J.
  2. (2004). eZPVE correction employing the RCCSD~T!/aug-cc-pVQZ harmonic vibrational frequencies obtained from the PEFs. 1816
  3. (2004). Some simulated SVL emission spectra, which contribute to the simulated ‘‘composite’’chemiluminescence spectrum @top trace same as Fig. 5~c!; see text#.
  4. (2004). to Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp
  5. (2009). to Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jsp4B.
  6. (2009). to Redistribution subject to AIP license or copyright; see http://jcp.aip.org/jcp/copyright.jspweak to assign. 4 Regarding the harmonic vibrational frequencies of the A ˜
  7. (2004). Weightsa ~present work! Weights ~Ref. 3! ~0,0,0! 0.15 0.65 ~0,0,1! 0.34 ~0,1,0! 0.10 0.20 ~0,0,2! 0.21 ~0,1,1! 0.02 ~0,2,0! 0.04 0.10 ~0,3,0! 0.01 0.05 ~1,0,0! 0.05 ~1,0,1! 0.09 aNormalized to unity. 1820

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