Failure of molecular dynamics to provide appropriate structures for quantum mechanical description of the aqueous chloride ion charge-transfer-to-solvent ultraviolet spectrum

Abstract

The lowest band in the experimental charge-transfer-to-solvent ultraviolet absorption spectrum of aqueous chloride ion is studied by experiment and computation. Interestingly, the experiments indicate that at concentrations up to at...

Observation of Solid–Liquid Phase Transitions of Brine Using the Far-Ultraviolet Charge-Transfer-to-Solvent Band

“…Most remarkably, the CTTS absorption of Cl – obeys Beer’s law up to the saturation concentration, and the molar absorption coefficient is 1.69 × 10 4 L/mol/cm. The value may be higher than the literature value of 1.2 × 10 4 L/mol/cm because the correction of the device function is suboptimal …”

“…The value may be higher than the literature value of 1.2 × 10 4 L/mol/cm because the correction of the device function is suboptimal. 27 The absorption of the first electron transition of H 2 O (A ̃← X ̃), with a maximum at approximately 145 nm, is also observed in Figure 3a. If no absorption directly derived from ions is observed, as in vibrational spectroscopy, the H 2 O absorptivity should decrease with increasing salt concentration.…”

“…Photoexcitation causes a vertical excitation from the hydrated anion state X – to a state comprising a neutral atom X, an emitted electron, the solvent, and its cavity. This is finally followed by stabilization, with the neutral atom inserted into the negatively charged solvent cavity, and this energy difference is currently interpreted as observed in the spectrum. − Apart from the validation of the models, numerous experimental studies regarding solvent effects and temperature dependence are also reported. − In the field of computer simulations, studies combining ab initio calculations with classical molecular dynamics searches for solvent structures are reported. − From an experimental perspective, with the spread of pulsed lasers, the focus has shifted to the dynamics of CT. , …”