Mg spin affects adenosinetriphosphate activity

The Schlegel-Frisch ab initio molecular dynamics (ADMP) (DFT:B3LYP), T = 310 K, is used to study complexation between adenosinetriphosphate (ATP), ATP subsystem, and magnesium cofactor [Mg(H2O)6]2+, Mg subsystem, in a water pool, modeled with 78 water molecules, in singlet (S) and triplet (T) states. The computations prove that the way of ATP cleavage is governed by the electron spin of Mg. In the S state Mg prefers chelation of \gamma-\beta-phosphate oxygens (O1-O2), whereas in the T state it chelates \beta-\alpha-phosphate oxygens (O2-O3) or produces a single-bonded intermediate. Unlike the chelates, which initiate ionic reaction paths, the single-bonded intermediate starts off a free-radical path of ATP cleavage, yielding a highly reactive adenosinemonophosphate ion-radical, .AMP-, earlier observed in the CIDNP (Chemically Induced Dynamic Nuclear Polarization) experiment (A.A. Tulub, 2006). The free-radical path is highly sensitive to Mg nuclear spin, which through a hyperfine interaction favors the production of unpaired electron spins. The unique role of Mg in ATP cleavage comes through its ability to serve as a unique redox center, initially accepting an electron from ATP and then giving it back to products. Redox activity of Mg differs for T and S states and affects the number of coordinated water molecules. The findings give a new insight into the NTP (N = nucleoside) energetics and assembly of NTP-operating molecules, including proteins.Comment: 13 pages, 4 figure

The Virial Theorem and the Ground State Problem in Polaron Theory

The virial theorem for the translation-invariant theory of a polaron [3] is discussed. It is shown that, in [3], Tulub made a nonoptimal choice of variational parameters in the strong-coupling limit, which led to the violation of the virial relations. The introduction of an additional variational parameter to the test function reduces the polaron energy and makes it possible to satisfy the relations of the virial theorem for a strong-coupling polaron (the Pekar 1 : 2 : 3 : 4 theorem)

Comments on "Translation-invariant bipolarons and the problem of high-temperature superconductivity"

We comment on the recent results of Refs. [1, 2] on the bipolaron problem derived using an approximation of Gross - Tulub. It is proved that, contrary to the claim made in Refs. [1, 2], the bipolaron ground state energy calculated there in the strong-coupling approximation has not been shown to constitute a variational upper bound.Comment: 3 pages, 2 figures, submitted to Solid State Communication

Reply to "On the cutoff parameter in the translation-invariant theory of the strong coupling polaron"

The present work is a reply to the paper [1]. It is proven that the argumentation of Ref. [1] is inconsistent. The variational functional for the polaron ground state energy considered in Ref. [1] contains an incomplete recoil energy. Since the variational functional of Ref. [1] is incomplete, it is not proven to provide a variational upper bound for the polaron ground-state energy. The same conclusion follows also for the bipolaron ground-state energy.Comment: 2 pages, 1 figure, submitted to Solid State Communication