OBSERVATIONS OF LOW-LYING ELECTRONIC STATES OF NiD, AND MULTI-ISOTOPE ANALYSIS

Ross, Amanda J.

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https://hdl.handle.net/2142/97171 Copy

Description

Title

OBSERVATIONS OF LOW-LYING ELECTRONIC STATES OF NiD, AND MULTI-ISOTOPE ANALYSIS

Author(s)

Ross, Amanda J.

Contributor(s)

• Crozet, Patrick
• Shayesteh, Alireza
• Abbasi, Mahdi

Issue Date

6/19/2017

Keyword(s)

Small molecules

Abstract

Resolved laser induced fluorescence spectra of NiD, recorded at Doppler resolution between 11500 and 18000 {cm$^{-1}$}, have _x000d_ defined some 200 term energies in two of the three strongly-interacting, low-lying ({$emph{X}~^2Delta$}, {$emph{W}~^2Pi$} and {$emph{V}~^2Sigma^+$}) states of NiD associated with an Ni${^+(3d^9}$)--D$^-$ configuration. _x000d_ Our observations span $v$,= 0,-,5 in the lowest spin-orbit component of the ground state, ${emph{X}_1~^2Delta_{5/2} }$, $v$,= 0,-,3 in _x000d_ {$emph{X}_2~^2Delta_{3/2}$ } and $v$,= 0,-,1 in ${emph{W}_1~^2Pi_{3/2} }$, the lower component of the {$emph{W}~^2Pi$ } state. _x000d_ Spin-orbit and rotation-electronic interactions are strong in NiD. Large parity splittings are seen, due to interactions with the unobserved _x000d_ $^2Sigma^+$ state. _x000d_ We have attempted a global, multi-isotope fit to reproduce observed term energies up to 6000 {cm$^{-1}$} in NiD and _x000d_ $^{58,60,62}$NiH, in an extension of the `Supermultiplet' model proposed by Gray and co-workers footnote{Gray, Li, Nelis, and Field, ${J.;Chem.;Phys.}$ underline{95}, _x000d_ 7164 (1991)}, because fits with NiD term energies alone failed to converge to sensible solutions. Dunham-type parameters have been used to represent the unperturbed {$emph{X}~^2Delta$ }, {$emph{W}_x000d_ ~^2Pi$ } and {$emph{V}~^2Sigma^+$ } states, with off-diagonal matrix elements (treating spin-orbit, $emph{L}$- and _x000d_ $emph{S}$-uncoupling effects) based on Ni$^+$ atomic properties. Some electronic Born-Oppenheimer breakdown terms were included in the model. _x000d_ _x000d_ _x000d_ The spectra show emission from several excited states close to the unique level populated by the single-mode laser. Bands of collisionally-induced fluorescence identify three levels (A ($Omega$,=,5/2) $v$,=,1, E ( $Omega$,=,3/2) $v$,=,1 and I ($Omega$,=,3/2) $v$,=,0) that have not been reported before.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/97171

DOI

10.15278/isms.2017.MH10

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