过饱和铝酸钠溶液中氢氧化铝自发成核动力学规律的研究

用电导法和吸光光度法首次对苛性比相同的不同浓度过饱和铝酸钠溶液自发分解过程进行了实时跟踪研究,获得铝酸钠溶解氢氧化铝自发成核动力学方程,探索了H₂O和Na⁺对氢氧化铝自发成核过程的影响.结果表明,过饱和铝酸钠溶液分解为氢氧化铝属化学反应控制过程;H₂O参与了溶液分解过程控制步骤的反应;K⁺和Na⁺等阳离子参与了溶液的重构,但对溶液分解的控制步骤影响不大.     

Adduct formation between alkali metal ions and anionic LV(V)O(2)(-) (L(2-) = tridentate ONS ligands) species: syntheses, structural investigation, and photochemical studies

Syntheses of alkali metal adducts [LVO(2)M(H(2)O)(n)] (1-7) (M = Na(+), K(+), Rb(+), and Cs(+); L = L(1)(-)L(3)) of anionic cis-dioxovanadium(V) species (LVO(2)(-)) of tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-(R-2-hydroxyphenyl))methyl)dithiocarbazate, R = H, L = L(1); R = NO(2), L = L(2); R = Br, L = L(3)) have been reported. The LVO(2)(-) moieties here behave like an analogue of carboxylate group and have displayed interesting variations in their binding pattern with the change in size of the alkali metal ions as revealed in the solid state from the X-ray crystallographic analysis of 1, 3, 6, and 7. The compounds have extended chain structures, forming ion channels, and are stabilized by strong Coulombic and hydrogen-bonded interactions. The number of coordinated water molecules in [LVO(2)M(H(2)O)(n)] decreases as the charge density on the alkali metal ion decreases (n = 3.5 for Na(+) and 1 for K(+) and Rb(+), while, for Cs(+), no coordinated water molecule is present). In solution, compounds 1-7 are stable in water and methanol, while in aprotic solvents of higher donor strengths, viz. CH(3)CN, DMF and DMSO, they undergo photoinduced reduction when exposed to visible light, yielding green solutions from their initial yellow color. The putative product is a mixed-oxidation (mu-oxo)divanadium(IV/V) species as revealed from EPR, electronic spectroscopy, dynamic (1)H NMR, and redox studies.     

Analysis of carrageenans by matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometry. I. kappa-Carrageenans.

Matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) mass spectra of small kappa-carrageenans are reported and discussed. MALDI spectra can be obtained in both positive and negative ion mode. In the absence of extraneous metal ions, positive ions are formed by the attachment of one Na(+) ion to the carrageenan, whereas for negative ions one Na(+) ion is detached from the sulfate group. Multiply charged species are not observed in MALDI. Intense ESI spectra can be obtained in negative ion mode and now multiply charged species are seen. Alkali exchange experiments show that in these small carrageenan anions one, but only one, alkali metal ion is bound in a bidentate coordination with two ionic sulfate groups. G2-type ab initio calculations on model ions HO(-) [M(+)] (-)OH (M = Li, Na, K, Cs), as well as arguments based on a simple Coulombic interaction model, show that the bidentate stabilization energy drops rapidly as the size of the alkali cation increases. Exchange of Na(+) with Li(+) leads to expulsion of the Na(+) ion generating, in ESI, intense multiply charged anions. An attempt is made to rationalize this behavior in terms of hydration effects.     

Cluster ions derived from sodium and potassium tetrafluoroborate and their collision induced dissociation in an ion trap mass spectrometer

Electrospray ionization was used to produce distributions of gas-phase cluster ions from solutions of sodium and potassium tetrafluoroborate. The majority of the cluster species followed the trend (MBF(4))(n)M(+), where M=Na and K. The values of n, for both salts, ranged from 1-15. Collision induced dissociation (MS/MS and MS(n)) in an ion trap mass spectrometer was used to determine the dissociation pathways for the cluster ions. The (NaBF(4))(n)Na(+) cluster ions fragmented via two pathways: (a) the loss of one or multiple neutral BF(3) molecules and (b) the loss of one or more NaBF(4) units. Of the two, the product ions corresponding to the loss of BF(3) units were more prominent. Unlike the Na salt, the (KBF(4))(n)K(+) cluster ions decomposed primarily by the loss of one or multiple KBF(4) units. Similar differences in dissociation behavior were observed when the heated transfer capillary, normally used to desolvate ions, was used to investigate cluster ion stability to thermal degradation and dissociation. The dissociation profiles (decrease in ion abundance with increasing activation amplitude) for several (NaF)(n)Na(+) and (KF)(n)K(+) cluster ions were measured and compared to probe the influence of the relative stability of the alkali fluorides (NaF and KF) on the dissociation behavior exhibited by the tetrafluoroborate cluster distributions. We found that the (NaF)(n)Na(+) cluster ions required higher activation amplitudes to induce fragmentation than the corresponding (KF)(n)K(+) species, indicative of stronger ionic bonding and higher gas-phase stability for the former. This in turn indicates that the reaction pathway involving only the loss of one or multiple units of BF(3), favored for the (NaBF(4))(n)Na(+) cluster series, but not for the analogous (KBF(4))(n)K(+) series, may be due to the high gas-phase stability of NaF, and relatively lower stability of KF, towards dissociation.     

Micro-Raman studies of hydrous ferrous sulfates and jarosites

Ferrous sulfates of various hydration states (FeSO(4) X xH(2)O; x=7, 4, 1) and jarosites (MFe(3)(SO(4))(2)(OH)(6); M=Na or K) were synthesized and studied by micro-Raman spectroscopy between 295 and 8K. Spectral analyses of the sulfate and water/hydroxyl vibrational modes are presented. Fingerprint regions attributed to the symmetric (nu(1)) and antisymmetric (nu(3)) stretching vibrations of the sulfate group are found to vary with the degree of hydration in hydrous ferrous sulfate. In jarosites, the Raman shift of the OH stretching mode is related to the type of alkali metal present between the tetrahedral and octahedral layers. The Raman technique can thus unambiguously identify ferrous sulfate of various hydration states and jarosites bearing different alkali metal ions.     

Study of ion specific interactions of alkali cations with dicarboxylate dianions

Alkali metal cations often show pronounced ion-specific interactions and selectivity with macromolecules in biological processes, colloids, and interfacial sciences, but a fundamental understanding about the underlying microscopic mechanism is still very limited. Here we report a direct probe of interactions between alkali metal cations (M(+)) and dicarboxylate dianions, (-)O(2)C(CH(2))(n)CO(2)(-) (D(n)(2-)) in the gas phase by combined photoelectron spectroscopy (PES) and ab initio electronic structure calculations on nine M(+)-D(n)(2-) complexes (M = Li, Na, K; n = 2, 4, 6). PES spectra show that the electron binding energy (EBE) decreases from Li(+) to Na(+) to K(+) for complexes of M(+)-D(2)(2-), whereas the order is Li(+) < Na(+) ≈ K(+) when M(+) interacts with a more flexible D(6)(2-) dianion. Theoretical modeling suggests that M(+) prefers to interact with both ends of the carboxylate -COO(-) groups by bending the flexible aliphatic backbone, and the local binding environments are found to depend upon backbone length n, carboxylate orientation, and the specific cation M(+). The observed variance of EBEs reflects how well each specific dicarboxylate dianion accommodates each M(+). This work demonstrates the delicate interplay among several factors (electrostatic interaction, size matching, and strain energy) that play critical roles in determining the structures and energetics of gaseous clusters as well as ion specificity and selectivity in solutions and biological systems.     

Cationic assembly of metal complex aggregates: structural diversity,solution stability,and magnetic properties

The tetradentate imino-carboxylate ligand [L](2)(-) chelates the equatorial sites of Ni(II) to give the complex [Ni(L)(MeOH)(2)] in which a Ni(II) center is bound in an octahedral coordination environment with MeOH ligands occupying the axial sites. Lanthanide (Ln) and Group II metal ions (M) template the aggregation of six [Ni(L)] fragments into the octahedral cage aggregates (M[Ni(L)](6))(x)(+) (1: M = Sr(II); x = 2,2: M = Ba(II); x = 2, 3: M = La(III); x = 3, 4: M = Ce(III); x = 3, 5: M = Pr(III); x = 3, and 6: M = Nd(III); x = 3). In the presence of Group I cations, however, aggregates composed of the alkali metal-oxide cations template various cage compounds. Thus, Na(+) forms the trigonal bipyramidal [Na(5)O](3+) core within a tricapped trigonal prismatic [Ni(L)](9) aggregate to give ((Na(5)O) subset [Ni(L)](9)(MeOH)(3))(BF(4))(2).OH.CH(3)OH, 7. Li(+) and Na(+) together form a mixed Li(+)/Na(+) core comprising distorted trigonal bipyramidal [Na(3)Li(2)O](3+) within an approximately anti-square prismatic [Ni(L)](8) cage in ((Na(3)Li(2)O) subset [Ni(L)](8)(CH(3)OH)(1.3)(BF(4))(0.7))(BF(4))(2.3).(CH(3)OH)(2.75).(C(4)H(10)O)(0.5), 8, while in the presence of Li(+), a tetrahedral [Li(4)O](2+) core within a hexanuclear open cage [Ni(L)](6) in ((Li(4)O) subset [Ni(L)](6)(CH(3)OH)(3))2ClO(4).1.85CH(3)OH, 9, is produced. In the presence of H(2)O, the Cs(+) cation induces the aggregation of the [Ni(L)(H(2)O)(2)] monomer to give the cluster Cs(2)[Ni(L)(H(2)O)(2)](6).2I.4CH(3)OH.5.25H(2)O, 10. Analysis by electronic spectroscopy and mass spectrometry indicates that in solution the trend in stability follows the order 1-6 > 7 > 8 approximately 9. Magnetic susceptibility data indicate that there is net antiferromagnetic exchange between magnetic centers within the cages.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

The influence of Al(III) supersaturation and NaOH concentration on the rate of crystallization of Al(OH)3 precursor particles from sodium aluminate solutions

The growth kinetics of colloidal Al(III)-containing particles (diameter<1000 nm), nucleated in optically clear, supersaturated sodium aluminate solutions as a precursor to Al(OH)(3) crystals, has been studied using dynamic light scattering. Two series of solutions were examined at 22 degrees C to determine the influence of Al(III) supersaturation and NaOH concentration on the initial particle growth behavior. One solution series consisted of solutions with constant Al(III) absolute supersaturation (DeltaC) of 1.48 M and [NaOH] range 1.83-4.00 M ([NaOH]/[Al(III)]=1.13-2.15) and Al(III) relative supersaturation (sigma)=3.86-10.36. The other solution series had a constant sigma of 7.55 and [NaOH] range of 1.50-4.27 M ([NaOH]/[Al(III)]=1.18-1.54) and DeltaC=0.86-3.19. The correlation between the initial particle growth rates and supersaturation (DeltaC or sigma) revealed marked anomalies over the entire supersaturation range studied. The growth rate remained substantially constant in the DeltaC range 0.86-2.55 M (for the constant sigma solution series), before increasing sharply upon a further increase of DeltaC beyond 2.55 M. The variation of the growth rate with sigma in the range 3.86-9.00 (for the constant DeltaC solution series) was remarkably weak, contrary to expectation. At higher sigma (>9.00), however, a marked increase in growth rate with increasing sigma was displayed. At constant DeltaC or sigma, the growth rate showed a strong variation with NaOH concentration, indicating that Na(+) and OH(-) species play a pivotal role in the Al(OH) precursor particles (nuclei) growth process. Furthermore, the kinetics of growth displayed by these nanosized particles are an order of magnitude slower than those observed for macroscopic gibbsite (gamma-Al(OH)(3)) crystals at similar supersaturations and temperature. The difference may be rationalized in terms of particle size and Al(OH)(3) dimorphic phase dependent solubility effects. An empirically adequate growth kinetics modeling was achieved when the growth rates were correlated with the Al(III) supersaturation (DeltaC or sigma) and the excess (free) NaOH concentration, rather than the former alone, as is commonly the case. A critical [NaOH]/[Al(III)] molar ratio of 1.27-1.35, below which the particle growth rate increased markedly and above which the rate was significantly reduced, was observed. This behavior is believed to be linked to solution speciation change that occurs at certain Al(III) and NaOH compositions.     

Theoretical studies on the electronic structure, charge distribution and vibrational spectra of diglyme-M(+)-AsF(6)(-) (M=Li, Na, K)

Electronic structure and the vibrational spectra of CH(3)(OCH(2)CH(2))(2)OCH(3)-M(+)-AsF(6)(-) (M=Li, Na, K) have been obtained using the density functional theory. Lithium ion exhibits a pentavalent coordination via 3 oxygens from diglyme and two fluorines of AsF(6)(-) whereas Na(+) and K(+) exhibit coordinate number 6 with 3 fluorines of the anion binding to alkali metal in these complexes. Analysis of calculated spectra reveal that the CH(2) wag (840-1120 cm(-1)) vibrations in the complex are sensitive to metal ion coordination. A frequency downshift relative to the free anion has been predicted for the vibrations of AsF(6)(-) anion when the fluorines are directly bonded (denoted by F) to metal ion. Consequent reorganization of electron density in the complex engenders a frequency shift in the opposite direction for As-F vibrations wherein the fluorine atoms are not coordinating to the alkali metal ion. An approach based on the molecular electron density topography coupled with the difference electron density map explains the direction of the frequency shifts of C-O-C and the As-F stretchings compared to those of free diglyme or AsF(6) anion. A new method, which includes the color-mapping function for the difference molecular electron density (MED), superimposed on the bond critical points in MED topography has been suggested to explain the direction of the frequency shifts in a single attempt.     

Extraction of sodium and potassium perchlorates with benzo-18-crown-6 into various organic solvents. Quantitative elucidation of anion effects on the extraction-ability and -selectivity for Na(+) and K(+)

To investigate quantitatively the anion effect on the extraction-ability and -selectivity of benzo-18-crown-6 (B18C6) for alkali metal ions, the constants for overall extraction into various diluents having low dielectric constants (K(ex)) and aqueous ion-pair formation (K(MLA)) of B18C6-sodium and potassium perchlorate 1:1:1 complexes (MLA) were determined at 25 degrees C. The K(ex) value was analyzed by the four fundamental equilibrium constants. The K(MLA) values were determined by applying our established method to this perchlorate extraction system. The K(M(B18C6)A) value of the perchlorate is much larger for K(+) than for Na(+), and is much smaller than that of the picrate. The K(M(B18C6)A) value makes a minor contribution to the magnitude of K(ex) for the perchlorate system, but a major contribution to that for the picrate one. The distribution behavior of the B18C6 1:1:1 complexes with the alkali metal perchlorates follows the regular solution theory. For the diluent with a high dipole moment, however, the 1:1:1 complexes somewhat undergo the dipole-dipole interaction. B18C6 always shows very high extraction selectivity for KClO(4) over NaClO(4), which is determined mostly by the much greater log/(log K(MLA)) value for K(+) than for Na(+). The extraction-ability and -selectivity of B18C6 for Na(+) and K(+) ions with a perchlorate ion were compared with those with a picrate ion in terms of the fundamental equilibrium constants. The K(+) extraction-selectivity of B18C6 over Na(+) for the perchlorate system is superior to that for the picrate one, which is caused largely by the greater log/(log K(K(B18C6)A))-log/(log K(Na(B18C6)A)) value for the perchlorate than for the picrate. The perchlorate system is recommended for extraction separation of K(+) from Na(+).     

Structural analysis of the solid amorphous binuclear complexes of iron(III) and aluminum(III) with chromium(III)-DTPA chelator using energy dispersive X-ray diffraction

This paper is concerned with the structural data obtained for two amorphous binuclear complexes of iron(III) and aluminum(III) with chromium(III)-diethylentriaminepentaacetic acid (chromium(III)-DTPA, CrL(2)(-)) using the energy-dispersive X-ray diffraction technique. Fe(OH)CrL(H(2)O)(6) and Al(OH)CrL(H(2)O)(6) are binuclear complexes, the metals ions being bridged via oxygen atoms. The metal ions are all octahedrally coordinated.     

UV and IR spectroscopic studies of cold alkali metal ion-crown ether complexes in the gas phase

We report UV photodissociation (UVPD) and IR-UV double-resonance spectra of dibenzo-18-crown-6 (DB18C6) complexes with alkali metal ions (Li(+), Na(+), K(+), Rb(+), and Cs(+)) in a cold, 22-pole ion trap. All the complexes show a number of vibronically resolved UV bands in the 36,000-38,000 cm(-1) region. The Li(+) and Na(+) complexes each exhibit two stable conformations in the cold ion trap (as verified by IR-UV double resonance), whereas the K(+), Rb(+), and Cs(+) complexes exist in a single conformation. We analyze the structure of the conformers with the aid of density functional theory (DFT) calculations. In the Li(+) and Na(+) complexes, DB18C6 distorts the ether ring to fit the cavity size to the small diameter of Li(+) and Na(+). In the complexes with K(+), Rb(+), and Cs(+), DB18C6 adopts a boat-type (C(2v)) open conformation. The K(+) ion is captured in the cavity of the open conformer thanks to the optimum matching between the cavity size and the ion diameter. The Rb(+) and Cs(+) ions sit on top of the ether ring because they are too large to enter the cavity of the open conformer. According to time-dependent DFT calculations, complexes that are highly distorted to hold metal ions open the ether ring upon S(1)-S(0) excitation, and this is confirmed by extensive low-frequency progressions in the UVPD spectra.     

Countercations direct one- or two-electron oxidation of an Al(III) complex and Al(III)-oxo intermediates activate C-H bonds

Hydrogen abstraction by aluminum(III)-oxo intermediates via reaction pathways reminiscent of late transition metal chemistry has been observed. Oxidation of M(+)[(IP(2-))(2)Al](-) (IP = iminopyridine, M = Na, Bu(4)N) yielded [Na(THF)(DME)][(IP(-))(IP(2-))Al(OH)] (3) or [(IP(-))(2)Al(OH)] (4), via O-atom transfer and subsequent C-H activation or proton abstraction, respectively.     

Probing ionophore selectivity in argon-tagged hydrated alkali metal ion-crown ether systems

Crown ethers are an important family of compounds that are closely related to naturally occurring ionophores. Thus, crown ethers are useful in modeling the size-selective behavior of ionophores. Using a combination of infrared predissociation spectroscopy and density functional theory calculations, we have investigated M(+)(18-crown-6 ether)(H(2)O)(1-4) Ar complexes, where M = Li, Na, K, Rb and Cs in the gas phase. The argon-tagging technique was used to lower the internal energies (effective temperatures ~100 K), yielding well-resolved spectra in the OH stretching region for systems containing up to three waters. Spectral changes were monitored as both the size of the ion and degree of hydration were varied. While there is not a particular spectroscopic signature of gas-phase selectivity reported in this work, the unique role that K(+) plays in the systems studied, as a "bridge" between the smaller and larger alkali metal ions, is consistent with the well-known special affinity for K(+) by 18-crown-6 ether in the aqueous phase.     

Unusual visible luminescence of aluminium polyoxocations in aqueous solution

Identification of aluminium polyoxocations, MO(4)Al(12)(OH)(24)(H(2)O)(12)(7/8+) (M = Al, Ga and Ge) (K-MAl(12)) and Al(30)O(8)(OH)(56)(H(2)O)(26)(18+) (Al(30)), by their luminescence is reported. The fluorescence behavior of K-Al(13) has been found to differ with different metal ions and anions, implying a new discovery of a potential ion sensor.     

Effects of central metal ions on vibrational circular dichroism spectra of tris-(beta-diketonato)metal(III) complexes

Vibrational circular dichroism (VCD) spectra of a series of [M(III)(acac)3] (acac = acetylacetonato; M = Cr, Co, Ru, Rh, Ir, and Al) and [M(III)(acac)2(dbm)] (dbm = dibenzoylmethanato; M = Cr, Co, and Ru) have been investigated experimentally and/or theoretically in order to see the effect of the central metal ion on the vibrational dynamics of ligands. The optical antipodes give the mirror-imaged spectra in the region of 1700-1000 cm(-1). The remarkable effect of the central metal ion is observed experimentally on the VCD peaks due to C-O stretches (1500-1300 cm(-1)) for both [M(III)(acac)3] and [M(III)(acac)2(dbm)]. In the case of Delta-[M(III)(acac)3], for example, the order of frequency of two C-O stretches (E and A2 symmetries) is dependent on the kind of a central metal ion as follows: E (-) > A2 (+) for M = Co, Rh, and Ir, while A2 (+) > E (-) for M = Cr and Ru. In the case of Delta-[M(III)(acac)2(dbm)], the order of frequency of three C-O stretches (A, B, and B symmetries) is as follows: A (-) > B (+) > B (+) for Co(III), B (+) > A (-) > B (-) for Cr(III), and A (-) > B (+) > B (-) for Ru(III). These results imply that the energy levels of C-O stretches are delicately affected by the kind of central metal ion. Since such detailed information is not obtained from the IR spectra alone, the VCD spectrum can probe the effect of the central metal ion on interligand cooperative vibration modes.     

Electronic effect on protonated hydrogen-bonded imidazole trimer and corresponding derivatives cationized by alkali metals (Li(+), Na(+), and K(+))

The electronic effects on the protonated hydrogen-bonded imidazole trimer (Im)(3)H(+) and the derivatives cationized by alkali metals (Li(+), Na(+), and K(+)) are investigated using B3LYP method in conjunction with the 6-311+G( *) basis set. The prominent characteristics of (Im)(3)H(+) on reduction are the backflow of the transferred proton to its original fragment and the remoteness of the H atom from the attached side bare N atom. The proton transfer occurs on both reduction and oxidation for the corresponding hydrogen-bonded imidazole trimer. For the derivatives cationized by Li(+), (Im)(3)Li(+), the backflow of the transferred proton occurs on reduction. The electron detachment from respective highest occupied molecular orbital of (Im)(3)Na(+) and (Im)(3)K(+) causes the proton transferring from the fragment attached by the alkali metal cation to the middle one. The order of the adiabatic ionization potentials of (Im)(3)M(+) is (Im)(3)H(+)>(Im)(3)Li(+)>(Im)(3)Na(+)>(Im)(3)K(+); the order of (Im)(3)M indicates that (Im)(3)H is the easicst complex to be ionized. The polarity of (Im)(3)M(+) (M denotes H, Li, Na, and K) increases on both oxidation and reduction. The (Im)(3)M(+) complexes dissociate into (Im)(3) and M(+) except (Im)(3)H(+), which dissociates preferably into (Im)(3) (+) and H atom, while the neutral complexes [(Im)(3)M] dissociate into (Im)(3) and M. The stabilization energy of (Im)(3)Li(2+), (Im)(3)Na(2+), and (Im)(3)K(2+) indicate that their energies are higher as compared to those of the monomers.     

Dissection of the difference between the group I metal ions in inhibiting GSK3β: a computational study

Glycogen synthase kinase 3β (GSK3β) is a serine/threonine kinase that requires two cofactor Mg(2+) ions for catalysis in regulating many important cellular signals. Experimentally, Li(+) is a competitive inhibitor of GSK3β relative to Mg(2+), while this mechanism is not experienced with other group I metal ions. Herein, we use native Mg(2)(2+)-Mg(1)(2+) GSK3β and its Mg(2)(2+)-M(1)(+) (M = Li, Na, K, and Rb) derivatives to investigate the effect of metal ion substitution on the mechanism of inhibition through two-layer ONIOM-based quantum mechanics/molecular mechanics (QM/MM) calculations and molecular dynamics (MD) simulations. The results of ONIOM calculations elucidate that the interaction of Na(+), K(+), and Rb(+) with ATP is weaker compared to that of Mg(2+) and Li(+) with ATP, and the critical triphosphate moiety of ATP undergoes a large conformational change in the Na(+), K(+), and Rb(+) substituted systems. As a result, the three metal ions (Na(+), K(+), and Rb(+)) are not stable and depart from the active site, while Mg(2+) and Li(+) can stabilize in the active site, evident in MD simulations. Comparisons of Mg(2)(2+)-Mg(1)(2+) and Mg(2)(2+)-Li(1)(+) systems reveal that the inline phosphor-transfer of ATP and the two conserved hydrogen bonds between Lys85 and ATP, together with the electrostatic potential at the Li(1)(+) site, are disrupted in the Mg(2)(2+)-Li(1)(+) system. These computational results highlight the possible mechanism why Li(+) inhibits GSK3β.