Ab Initio Study of the Phosphorescence of Nitrite Ions |
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Authors: | B F Minaev V A Minaeva |
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Institution: | (1) Cherkassy Engineering and Technological Institute, 257006 Cherkassy, Ukraine;(2) Cherkassy State University, 257001 Cherkassy, Ukraine |
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Abstract: | In order to interpret the phosphorescence spectra of NaNO2 and similar single crystals, we performed MCSCF geometry optimization in the ground singlet (X
1
A
1) and in the first excited triplet (a
3
B
1) states of the NO
2
-
ion and MCSCF quadratic response (QR) calculation of the a
3
B
1–X
1
A
1 transition probability at different bending angles and asymmetric stretch modes. The complete form of the spin–orbit coupling (SOC) operator is accounted for in the QR procedure. Dunning's correlation-consistent polarized valence double- (cc-pVDZ) and triple- (cc-pVTZ) basis sets are imployed. The electric-dipole transition moment from the T
z spin sublevel (z is the C
2 axis) oriented along the y direction (the other in-plane axis) is found to be 5 times higher than that from the T
y sublevel in the ground-state geometry. This is in agreement with polarization measurements and with optical detection of ESR spectra. The T
z–S
0 transition moment decreases almost linearly with an increase in the ONO bond angle. The so-called non-Condon effects in the phosphorescence spectra of NaNO2 crystals are explained on these backgrounds. The long progression of the bending vibrations (v
2, a
1) with an anomolous intensity distribution in the T
z–S
0 transition and additional involvement of the asymmetric stretch mode (v
3, b
2) in the T
y–S
0 transition are interpreted by force field and SOC calculations in the MCSCF-response technique. Configuration interaction (CI) calculations of the spin-allowed electric dipole transitions in NO
2
-
ions with effective one-electron SOC operator matrix element estimations were done for comparison with the results of the quadratic and linear response methods. Other T
n–S
0 transitions are also studied. Finally, a short discussion of nonradiative processes is presented. |
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Keywords: | Phosphorescence nitrite ions ab initio study |
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