A Dynamic Model to Explain Hydration Behaviour along the Lanthanide Series

Fragment Molecular Orbital-Based Molecular Dynamics Study on Hydrated Ln(III) Ions

“…These observations are in line with the RDF results (Fig. 4), again indicating that the gadolinium break [8][9][10][11][12] is not a sudden but smooth change in the hydrations of intermediate Ln(III) [24,27]. …”

“…5 plots the ADFs of La(III) and Lu(III). The first peak positions are in accord with the characteristic TTP and SAP structures [12,22,24,27], as expected. The shape of the first peak of Lu(III) is sharper than that of La(III), suggesting the tighter frame of the former.…”

“…It is notable that both La-O length and Lu-O length are shortened relative to the cluster results [37], indicating the influence of outer sphere waters. This consideration is supported by the fact that our preliminary FMO-MD result with [La(H 2 O) 24 ] 3+ provided 2.61 Å as the La-O length [37]. The present HF-based MD Figs.…”

“…So far, an amount of simulations covering classical molecular mechanical (MM) MD, quantum mechanical (QM) and plane-wave type Car-Parrinello MD (CPMD) [16] and hybrid QM/MM MD have been reported on the hydrated Ln(III) ions [17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. A notable merit of CPMD is that it can directly handle electronic properties [17,18,23,29] at sizable computational costs.…”

“…In contrast, systematic comparison of several Ln(III) ions is straightforward for MM or QM/MM schemes with much lower costs per step. Duvail et al [24] performed a series of MM MD for all Ln(III) ions and found that there is a crossover change in dominant coordination from nine to eight between Tb and Dy. They also pointed out the existence of an intermediate bi- In this proceeding, we report a series of MD simulation based on the fragment molecular orbital (FMO) method [35], termed as FMO-MD [36], for the hydrated Ln(III) ions.…”