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Title: A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3

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 2A" π radical state, with a 6π-electron, 2A', σ radical state being at most ~1.0 kcal/mol higher in energy. This assignment contrasts with our recent finding that the ground state of P2N3• is a 6π-electron σ radical state

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1340802
Report Number(s):
PNNL-SA-118787
Journal ID: ISSN 1089-5639; 49062; KC0301050
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory; Journal Volume: 120; Journal Issue: 31
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Hou, Gao-Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, and Wang, Xue-Bin. A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b06343.
Hou, Gao-Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, & Wang, Xue-Bin. A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –. United States. doi:10.1021/acs.jpca.6b06343.
Hou, Gao-Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, and Wang, Xue-Bin. Thu . "A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –". United States. doi:10.1021/acs.jpca.6b06343.
@article{osti_1340802,
title = {A Joint Experimental and Computational Study of the Negative Ion Photoelectron Spectroscopy of the 1-Phospha-2,3,4-triazolate Anion, HCPN 3 –},
author = {Hou, Gao-Lei and Chen, Bo and Transue, Wesley J. and Hrovat, David A. and Cummins, Christopher C. and Borden, Weston Thatcher and Wang, Xue-Bin},
abstractNote = {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 2A" π radical state, with a 6π-electron, 2A', σ radical state being at most ~1.0 kcal/mol higher in energy. This assignment contrasts with our recent finding that the ground state of P2N3• is a 6π-electron σ radical state},
doi = {10.1021/acs.jpca.6b06343},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 31,
volume = 120,
place = {United States},
year = {Thu Aug 11 00:00:00 EDT 2016},
month = {Thu Aug 11 00:00:00 EDT 2016}
}