This work presents a thermodynamic method for treating nonequilibrium solvation. By imposing an extra electric field onto the nonequilibrium solvation system, a virtual constrained equilibrium state is prepared. In this way, the free energy difference between the real nonequilibrium state and the con-strained equilibrium one is simply the potential energy of the nonequilibrium polarization in the extra electronic field, according to thermodynamics. Further, new expressions of nonequilibrium solvation energy and solvent reorganization energy have been formulated. Analysis shows that the present formulations will give a value of reorganization energy about one half of the traditional Marcus theory in polar solvents, thus the explanation on why the traditional theory tends to overestimate this quantity has been found out. For the purpose of numerical determination of solvent reorganization energy, we have modified Gamess program on the basis of dielectric polarizable continuum model. Applying the procedure to the well-investigated intramolecular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy have been found to be in good agreement with the experimental fittings.
LI XiangYuanWANG JingBoMA JianYiFU KeXiangHE FuCheng
A few open-shell molecules are taken as examples in order to examine the performance of the open-shell perturbation theory for electron correlation(J Chem Theory Comput,2009,5:931–936).The convergence of the perturbation series is shown to be stable for the doublet state of NH2 at both the equilibrium and stretched geometries.The equilibrium bond lengths,and harmonic and anharmonic vibrational frequencies are calculated for NO(X2),OH(X2),CH(X2)and NH(X2)with different second-order perturbation theories at the cc-pVDZ,cc-pVTZ and cc-pVQZ levels.The ground state energies of BeF(X2+), MgH(X2+)and the HCCl triplet state have also been computed with various perturbation theories and compared with configuration interaction with single and double excitations(CISD)and CISD+Davidson correction.The energy difference between the formaldehyde(H2CO + )and hydroxymethylene(HCOH+)radical cations has been computed.Our perturbation theory predicts correctly that H2CO + is more stable than HCOH+.However,calculations using UMP2,CASPT2,the Z-averaged perturbation theory and restricted Mφller–Plesset theory fail even to produce the correct sign of the energy difference.
The low-lying electronic states of Yb and YbO are investigated by using time-dependent relativistic density functional theory,which is based on the newly developed exact two-component Hamiltonian resulting from symmetrized elimination of the small component.The nature of the excited states is analyzed by using the full molecular symmetry.The calculated results support the previous experimental assignment of the ground and excited states of YbO.
