On optical dispersion in transparent molecular systems

Hauser, U.; Oestreich, V.; Rohrweck, Heinz Dieter

doi:10.1007/bf01433868

Cited by 47 publications

(13 citation statements)

References 8 publications

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“…Mössbauer parameters obtained from deconvolution of the spectra assuming a model with a quadrupole doublet are listed in Table 1 (i). The parameters (I. S. and Q. S.) for the SPN/NaCl disk agreed with the known Mössbauer parameters for SPN [3][4][5]12,13], whereas the line-width for the irradiated disk was remarkably larger than those for the disk before irradiation and after annealing. Hence, the spectrum can also be deconvoluted to one quadrupole doublet ascribed to SPN and two others; another model with three pairs of quadrupole doublets.…”

Section: Visual Observationsupporting

confidence: 69%

“…= -0.183 mm/s relative to Fe(Pd) source; Q.S. = 2.736 mm/s) reported for the metastable state produced by irradiation at 400-530 nm [3][4][5]. Hence, it is obvious that the photoexcited product produced by UV irradiation at 300-400 nm in this work is different from the metastable state produced previously by irradiation with visible light.…”

Section: Visual Observationcontrasting

confidence: 65%

See 1 more Smart Citation

Mössbauer and ESR Study of Long-Lived Photoexcited Species in Sodium Pentacyanonitrosylferrate( ll) Produced by 300-400 NM UV Irradiation at Low Temperatures

et al. 1986

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Na 2 [Fe(CN) S (NO)]· 2 H,0/UV irradiation/Excited species/ Mössbauer I ESR AbstractThe color of sodium pentacyanonitrosylferrate(Il) dispersed in alkali halide disk changed to dark brown with UV (300-400 nm) irradiation at 78 Κ and remained unchanged for at least one day at 78 K. However, the original color of the salt quickly returned after annealing. The long-lived photoexcited state was characterized by means of Fe-57 Mössbauer technique and electron spin resonance.

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Section: Visual Observationsupporting

confidence: 69%

Section: Visual Observationcontrasting

confidence: 65%

Mössbauer and ESR Study of Long-Lived Photoexcited Species in Sodium Pentacyanonitrosylferrate( ll) Produced by 300-400 NM UV Irradiation at Low Temperatures

et al. 1986

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“…They are types of excited molecular state and are distinguished from the ground state by their thermal and spectroscopic properties. [1][2][3][4][5] The metastable states are believed to be caused by the chargetransfer from the iron d orbital to the nitrosyl π* orbital, and characterized by the notably downshifted ν(NO) frequencies. 4,6 Similar metastable states have been found in several nitrosylruthenium and nitrosyl-osmium complexes.…”

Section: Introductionmentioning

confidence: 99%

Light-induced metastable states in nitrosyl–ruthenium complexes containing ethylenediamine and oxalate ion ligands

Morioka

Ishikawa

Tomizawa

et al. 2000

J. Chem. Soc., Dalton Trans.

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The metastable state which is produced by irradiation with the green-blue region of light was studied by IR and other spectroscopic techniques for solid states of newly synthesized nitrosyl-ruthenium complexes; cis-[Ru(Hox)-. Continued irradiation at 77 K results in development of a photostationary state in the same way as for sodium nitroprusside. The population of the metastable state molecule in the photostationary state of each sample depends on the irradiation wavelength and reaches a maximum at 441.6 nm which is the shortest wavelength in the present study. A broad absorption band with an absorbance maximum at ≈600 nm is observed for the metastable state of a trans-[Ru(Hox)(en) 2 NO]Cl 2 single crystal. The short wavelength tail of the band is considered to be involved in the photostationary equilibrium under blue light radiation. The metastable state molecules decay to the ground state at temperatures considerably higher than the two metastable molecules (MS 1 and MS 2 ) of sodium nitroprusside. The decay temperature of trans-[Ru(Hox)(en) 2 NO]Cl 2 , which is defined as the temperature at which the rate constants of the thermal decay becomes 10 Ϫ3 s Ϫ1 , is 277 K, which is the highest value reached among the metastable states of nitrosyl complexes reported so far. In the Raman spectra of trans-[Ru(Hox)(en) 2 NO]Cl 2 , the Ru-(NO) stretching vibrations are observed at 604 cm Ϫ1 and 476 cm Ϫ1 for the ground and metastable state molecules, respectively. ExperimentalThe starting material [Ru(ox)(en) 2 ][Ru(ox) 2 (en)] was prepared according to the procedure of Broomhead and Kane-Maguire. 17 A mixture of cis-[Ru(Hox)(en) 2 NO]Cl 2 ؒEtOH (abbreviated to 1a, hereafter), cis-K[Ru(ox) 2 (en)NO]ؒ3H 2 O (2), cis-[Ru(Hox)(ox)(en)NO] (3), and cis-K[Ru(ox) 2 (en)NO] (4) was obtained from [Ru(ox)(en) 2 ][Ru(ox) 2 (en)] treated with NO gas in an acidic solution, and the complexes were separated and purified by ion exchange column chromatography (SP-Sephadex C-25 and QAE-Sephadex A-25).

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“…We seek to avoid the ambiguities of peak assignment described above by applying 2D IR to cavitycoupled sodium nitroprusside (SNP). The vibrational spectroscopy, dynamics, photochemistry [27][28][29][30][31][32] , and implementation of SNP in optical devices [33][34][35][36][37][38][39][40] have been studied; furthermore, SNP is a prototypical system for studying photoinduced metal-nitrosyl linkage isomerism 32 . Critical to this work, SNP has a similar molecular structure to W(CO) 6 and Fe(CN) 6 3but with a nondegenerate NO stretching vibrational mode suitable for strong coupling (Fig.…”

Section: Introductionmentioning

confidence: 99%

Excited-State Vibration-Polariton Transitions and Dynamics in Nitroprusside

Grafton¹,

Dunkelberger²,

Simpkins³

et al. 2020

Preprint

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<div> <div> <div> <p>Strong cavity coupling to molecular vibrations creates vibration-polaritons capable of modifying chemical reaction kinetics, product branching ratios, and charge transfer equilibria. However, the mechanisms impacting these molecular processes remain elusive. Furthermore, even basic elements determining the spectral properties of polaritons, such as selection rules, transition moments, and lifetimes, are poorly understood. Here, we use two-dimensional infrared and filtered pump–probe spectroscopy to report clear spectroscopic signatures and relaxation dynamics of excited vibration-polaritons formed from the cavity- coupled NO band of nitroprusside. We apply a multi-level quantum Rabi model that predicts transition frequencies and strengths that agree very well with our experiment. Notably, the polariton features decay ~3-4 times slower than the polariton dephasing time, indicating that they support incoherent population, a consequence of their partial matter character. Understanding the factors determining polariton population and dephasing lifetimes will impact polariton-modified energy transfer, photophysics, and chemistry. </p> </div> </div> </div>

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On optical dispersion in transparent molecular systems

Cited by 47 publications

References 8 publications

Mössbauer and ESR Study of Long-Lived Photoexcited Species in Sodium Pentacyanonitrosylferrate( ll) Produced by 300-400 NM UV Irradiation at Low Temperatures

Mössbauer and ESR Study of Long-Lived Photoexcited Species in Sodium Pentacyanonitrosylferrate( ll) Produced by 300-400 NM UV Irradiation at Low Temperatures

Light-induced metastable states in nitrosyl–ruthenium complexes containing ethylenediamine and oxalate ion ligands

Excited-State Vibration-Polariton Transitions and Dynamics in Nitroprusside

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