Vibrational spectra and normal coordinate analysis of difluorophosphine‐d0 and ‐d1

During, James R.; Zozulin, A. J.; Odom, J. D.; Streusand, B. J.

doi:10.1002/jrs.1250080509

Cited by 7 publications

(4 citation statements)

References 9 publications

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“…h Unimolecular rate constant for nonradiative decay, calculated by using eq 4 in the text. 1 Data for a slurry of HUP in its mother liquor, the filtrate from its synthesis; emission from the mother liquor was negligible at 295 K. We believe that the measured lifetime for the slurry is a more reliable value and that the discrepancy from the value of for the solid indicates degradation of the solid under our experimental conditions (see Results and Discussion and Experimental Section). For the measurement of the solid, degradation did not appear to be a problem owing to the much lower excitation intensity employed.…”

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confidence: 76%

“…The excited-state properties of inorganic solids are receiving considerable attention as a means of characterizing electronic structure and physical processes occurring within the solid. Useful applications of luminescence, traditionally the basis for such studies, have included the design of phosphors1 and light-emitting diodes,2 as well as the characterization of semiconductor electrodes3 and colloids.4 Although numerous (1) Leverenz, H. W. "An Introduction to Luminescence of Solids"; Dover:…”

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confidence: 99%

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Excited-state properties of lamellar solids derived from hydrogen uranyl phosphate

Olken¹,

Biagioni²,

Ellis³

1983

Inorg. Chem.

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The excited-state properties of the layered compound hydrogen uranyl phosphate (HUP), HU02P04.4H20, and of solids derived therefrom have been examined; the derivatives, prepared by intercalative ion-exchange reactions, have compositions based on stoichiometric proton substitution by NH4+, pyridinium, n-butylammonium, n-octylammonium, K+, and Ag+, 0.5 equiv of Ca2+ and Zn2+, and 0.4 equiv of Cu2+. These compounds have all been characterized by elemental analysis, IR spectroscopy, and X-ray powder diffraction; the last confirms the retention of the lamellar structure upon cationic substitution and reveals that the interlamellar spacing can vary considerably with the choice of cation. All of the samples exhibit electronic absorption spectra characteristic of the UOZ2+ chromophore. Except for the n-octylammonium, Ag+ and Cu2+ salts, the samples all exhibit yellow-green emission characteristic of the UOZ2+ moiety when excited with blue or near-UV light at 295 K. Emission decay curves are exponential for all of the luminescent solids and yield lifetimes, T , ranging from -1 to 450 ps. HUP and its K+, NH4+, pyridinium, and CaZ+ derivatives are all highly emissive with measured radiative quantum efficiencies, @, , approaching unity at 295 K. Values of T and @, have been used to calculate radiative (k,) and nonradiative (k",) rate constants for excited-state decay. Values of k, are nearly constant at -(l-2) X lo3 s-] for the samples, whereas k , values span several orders of magnitude. Possible quenching mechanisms for the weakly emissive and nonemissive solids are described and compared with previously reported solution data.The excited-state properties of inorganic solids are receiving considerable attention as a means of characterizing electronic structure and physical processes occurring within the solid. light-emitting diodes,, as well as the characterization of semiconductor electrodes3 and colloid^.^ Although numerous Useful applications of luminescence, traditionally the basis for such studies, have included the design of phosphors' and (1) L~~~~~~~, H, W, -An ~~~~d~ to ~~~i~~~~~~~~ of Solids"; D~~~~ New York, 1968.

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confidence: 76%

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confidence: 99%

Excited-state properties of lamellar solids derived from hydrogen uranyl phosphate

Olken¹,

Biagioni²,

Ellis³

1983

Inorg. Chem.

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“…We have used the same procedure as that for PH 2 F and PH 2 Cl. The ground state rotational constants of PHF 2 and PDF 2 are taken from ref , and the harmonic force field, from ref . The ground state rotational constants of P 35 Cl 3 and P 37 Cl 3 are taken from ref , and the force field from ref .…”

Section: Determination Of the Structuresmentioning

confidence: 99%

Millimeter-Wave Spectra,ab InitioCalculations, and Structures of Fluorophosphane and Chlorophosphane

Dréan¹,

Paplewski²,

Demaison³

et al. 1996

Inorg. Chem.

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The structures of fluorophosphane, PH2F, and chlorophosphane, PH2Cl, have been calculated ab initio at the SCF, MP2, CCSD, and CCSD(T) levels using a quadruple ζ polarized basis set. Equilibrium and ground state rotational constants as well as centrifugal distortion constants have been predicted for several isotopomers of PH2F and PH2Cl. Theoretical CCSD(T) geometries were also determined for the series of PH n X3 - n (X = F, Cl; n = 0−3) molecules using a triple ζ polarized basis set. The millimeter-wave spectra of the short-lived molecules PH2F, PH2Cl, and their perdeuterated species were measured in the frequency range 100−470 GHz. For PH2F and PH2Cl, accurate ground state parameters have been obtained by a combined fit of the millimeter-wave data and the infrared ground state combination differences. The r o, r z, and r e structures of PH2F and PH2Cl, as well as PH3, PCl3, and PHF2 have been determined. The experimental results are found in excellent agreement with their ab initio predictions.

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“…Turning to individual molecules, the experimental frequencies for PH3 and PF3 are well established from high-resolution work.17-22 Two independent studies23,24 of PHF2 yield frequencies that agree to 2 cm-1 or better for v,, p2, p4, and ps but differ appreciably for the P-F stretching modes v3 and p6 (see Table VI, especially footnote e). We prefer the assignment of ref 24, which implies an error of 3 cm-1 in our calculated splitting between this pair of frequencies, whereas the assignment of ref 23 would imply an error of 26 cm-1, which seems unreasonably large in view of the general accuracy of such 6-31G** frequency splittings (see above and Table VI).…”

Section: Resultsmentioning

confidence: 87%

Ab initio calculation of harmonic force fields and vibrational spectra for the fluorophosphines PHnF3-n (n = O-3)

Breidung¹,

Thiel²

1988

J. Phys. Chem.

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Vibrational spectra and normal coordinate analysis of difluorophosphine‐d₀ and ‐d₁

Cited by 7 publications

References 9 publications

Excited-state properties of lamellar solids derived from hydrogen uranyl phosphate

Excited-state properties of lamellar solids derived from hydrogen uranyl phosphate

Millimeter-Wave Spectra,ab InitioCalculations, and Structures of Fluorophosphane and Chlorophosphane

Ab initio calculation of harmonic force fields and vibrational spectra for the fluorophosphines PHnF3-n (n = O-3)

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