title: A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN3(.).
abstract: We report here the results of a combined experimental and computational study of the negative ion photoelectron spectroscopy (NIPES) of the recently synthesized, planar, aromatic, HCPN3(-) ion. The adiabatic electron detachment energy of HCPN3(-) (electron affinity of HCPN3(•)) was measured to be 3.555 ± 0.010 eV, a value that is intermediate between the electron detachment energies of the closely related (CH)2N3(-) and P2N3(-) ions. High level electronic structure calculations and Franck-Condon factor (FCF) simulations reveal that transitions from the ground state of the anion to two nearly degenerate, low-lying, electronic states, of the neutral HCPN3(•) radical are responsible for the congested peaks at low binding energies in the NIPE spectrum. The best fit of the simulated NIPE spectrum to the experimental spectrum indicates that the ground state of HCPN3(•) is a 5π-electron (2)A″ π radical state, with a 6π-electron, (2)A', σ radical state being at most 1.0 kcal/mol higher in energy.
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory , P.O. Box 999, MS K8-88, Richland, Washington 99352, United States.
authors.forename: Gao-Lei
authors.initials: GL
authors.lastname: Hou
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Bo
authors.initials: B
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Wesley J
authors.initials: WJ
authors.lastname: Transue
authors.affiliation: Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas , 1155 Union Circle, #305070, Denton, Texas 76203-5017, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Hrovat
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
authors.affiliation: Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas , 1155 Union Circle, #305070, Denton, Texas 76203-5017, United States.
authors.forename: Weston Thatcher
authors.initials: WT
authors.lastname: Borden
authors.affiliation: Physical Sciences Division, Pacific Northwest National Laboratory , P.O. Box 999, MS K8-88, Richland, Washington 99352, United States.
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang