2014
DOI: 10.1021/jz501710c
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Vibrational Energy Relaxation of Thiocyanate Ions in Liquid-to-Supercritical Light and Heavy Water. A Fermi’s Golden Rule Analysis

Abstract: The vibrational relaxation dynamics following an ultrafast nitrile stretching (ν3) excitation of thiocyanate anions dissolved in light and heavy water have been studied over a wide temperature and density range corresponding to the aqueous liquid up to the supercritical phase. In both solvents, the relaxation of the ν3 = 1 state of the anion leads to a direct recovery of the vibrational ground state and involves the resonant transfer of the excess vibrational energy onto the solvent. In light water, the energy… Show more

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Cited by 23 publications
(39 citation statements)
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“…This is further supported by the blue-shift of the d HOH + n lib combination band owing to stronger hydrogen-bonding interactions stiffening the intermolecular potential concomitantly, thereby increasing the librational frequency. [31][32][33] In contrast, only the non-eutectic mixture develops the sharp, red-shifted peak in the n OD stretch region attributable to ice formation. From these experiments, it is clear that the eutectic mixture supercools and vitrifies into a glass at the known glasstransition temperature 140 K. 30 This is demonstrated by the continuous changes in the water (ice) lineshape (Fig.…”
Section: Discussionmentioning
confidence: 99%
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“…This is further supported by the blue-shift of the d HOH + n lib combination band owing to stronger hydrogen-bonding interactions stiffening the intermolecular potential concomitantly, thereby increasing the librational frequency. [31][32][33] In contrast, only the non-eutectic mixture develops the sharp, red-shifted peak in the n OD stretch region attributable to ice formation. From these experiments, it is clear that the eutectic mixture supercools and vitrifies into a glass at the known glasstransition temperature 140 K. 30 This is demonstrated by the continuous changes in the water (ice) lineshape (Fig.…”
Section: Discussionmentioning
confidence: 99%
“…The n CN stretch mode of SCN À has been shown to be a sensitive probe of its environment. 20,32,[37][38][39][40][41] At room temperature the n CN stretch band in LiCl-SCN mixtures peaks at 2070 cm À1 rather than at the 2055 cm À1 observed in fully water-solvated anions. This is consistent with the formation of Li + NCS À contact ion pairs (CIPs) as expected in solutions at high concentration.…”
Section: Discussionmentioning
confidence: 99%
“…24 Early MD simulations noted few linear hydrogen bonds with water 25 and many arrangements of dipolar character, while more recent MD simulations of SeCN -26 found an average of 3-4 hydrogen bonds, with one of them being an axial (linear) hydrogen bond. Ultrafast infrared spectroscopy has used the ν 3 mode of pseudo-halide anions to investigate ultrafast vibrational dynamics of water and other polar solvents, 23,[27][28][29][30][31][32] concentrated ion solutions, [33][34][35] ILs, [36][37][38][39][40] supported IL membranes, 41 and colloid emulsions. 42 Furthermore, a combination of MD simulations and ultrafast infrared spectroscopy developed a spectroscopic map of SeCNin D 2 O that describes the frequency dependence of the nitrile stretch to a hydrogen bonding environment.…”
Section: Introductionmentioning
confidence: 99%
“…24 Early MD simulations noted few linear hydrogen bonds with water 25 and many arrangements of dipolar character, while more recent MD simulations of SeCN -26 found an average of 3-4 hydrogen bonds, with one of them being an axial (linear) hydrogen bond. Ultrafast infrared spectroscopy has used the ν 3 mode of pseudo-halide anions to investigate ultrafast vibrational dynamics of water and other polar solvents, 23,[27][28][29][30][31][32] concentrated ion solutions, [33][34][35] ILs, [36][37][38][39][40] supported IL membranes, 41 and colloid emulsions. 42 Furthermore, a combination of MD simulations and ultrafast infrared spectroscopy developed a spectroscopic map of SeCNin D 2 O that describes the frequency dependence of the nitrile stretch to a hydrogen bonding environment.…”
Section: Introductionmentioning
confidence: 99%