1973
DOI: 10.1002/chin.197340003
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ChemInform Abstract: VIBRATIONAL SPECTRA OF SOME GROUP VB HALIDES PART 2, A RAMAN SPECTROSCOPIC STUDY OF HALOBISMUTHATE(III) AND HALOANTIMONATE(III) COMPLEXES IN HALOGEN ACID SOLUTIONS

Abstract: Die Raman‐Spektren der HBr‐ und HCl‐Lösungen von Bi(III) und Sb(III) werden aufgenommen und die bei verschiedenen Halogen‐Metall‐Verhältnissen gebildeten Spezies untersucht.

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“…Short-wavelength Δ A kinetic traces show modulations with a 121 cm –1 frequency (FFT) and a several picosecond decoherence lifetime (Figure c). These modulations can be assigned to the solute’s impulsive stimulated Raman scattering (ISRS) because they start at negative delay times as soon as excitation and probe pulses begin to temporally overlap and exhibit the frequency close to a 114 cm –1 a 1g Raman frequency of BiI 6 3– . , The long decoherence time also agrees with these modulations taking place in the BiI 6 3– electronic ground state. Different modulations with a frequency of ν 1 = 89 ± 2 cm –1 (FFT, 94 ± 12 cm –1 ; Figure S7 and Table S3) occur in-phase in the blue and red wings of the 625 nm Δ A band (from 535 to 625 and 760 nm; Figure d).…”
Section: Resultsmentioning
confidence: 67%
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“…Short-wavelength Δ A kinetic traces show modulations with a 121 cm –1 frequency (FFT) and a several picosecond decoherence lifetime (Figure c). These modulations can be assigned to the solute’s impulsive stimulated Raman scattering (ISRS) because they start at negative delay times as soon as excitation and probe pulses begin to temporally overlap and exhibit the frequency close to a 114 cm –1 a 1g Raman frequency of BiI 6 3– . , The long decoherence time also agrees with these modulations taking place in the BiI 6 3– electronic ground state. Different modulations with a frequency of ν 1 = 89 ± 2 cm –1 (FFT, 94 ± 12 cm –1 ; Figure S7 and Table S3) occur in-phase in the blue and red wings of the 625 nm Δ A band (from 535 to 625 and 760 nm; Figure d).…”
Section: Resultsmentioning
confidence: 67%
“…This rules out coherent vibrational motion taking place on the product PES because in this case the oscillations in the blue and red wings of the product absorption band should exhibit a sharp π-phase shift. , The constant phase of the oscillations suggests stepwise coherent population of the 3 π LMCT product state: coherent vibrational motion with a ∼92 cm –1 frequency (period, 360 fs) makes BiI 6 3– to revisit the coupling region between the 3 T 1u and 3 π LMCT states in an oscillatory, time-dependent fashion (Figure ). Tetragonal distortion and/or totally symmetric stretching are likely the motions involved in the 92 cm –1 reaction mode because the corresponding nuclear displacements, being Raman- and JT-active, are the earliest to occur following the excitation event and the observed frequency is close to the e g and a 1g frequencies in BiI 6 3– (96 and 114 cm –1 , , and the t 2g frequency is ∼2 times lower). It takes two approaches of the coupling zone for coherent transfer of the population into the 3 π LMCT, the first at ∼190 fs and the second at ∼550 fs; the oscillation maxima (∼4:1 ratio; Figure d) are related to the population fractions being transferred.…”
Section: Discussionmentioning
confidence: 86%
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