Search

Atomic multipole moments are used to investigate vibrational frequency shifts of CO and H2in uniform and inhomogeneous electric fields using ab initio calculations and Molecular Dynamics (MD) simulations. The importance of using atomic multipole moments that can accurately represent both molecular electrostatics and the vibrational response of the molecule to changes in the local electric field is highlighted. The vibrational response of CO to applied uniform and inhomogeneous electric fields is examined using Density Functional Theory calculations for a range of test fields, and the results are used to assess the performance of different atomic multipole models. In uniform fields, the calculated Stark tuning rates of Δμ = 0.52 cm−1/(MV/cm) (DFT), Δμ = 0.55 cm−1/(MV/cm) (fluctuating three-point charge model), and Δμ = 0.64 cm−1/(MV/cm) (Multipole model up to octupole), compare favorably with the experimentally measured value of 0.67 cm−1/(MV/cm). For H2, which has no permanent dipole moment, CCSD(T) calculations demonstrate the importance of bond-weakening effects in force fields in response to the applied inhomogeneous electric field. Finally, CO in hexagonal ice is considered as a test system to highlight the performance of selected multipolar models in MD simulations. The approach discussed here can be applied to calibrate a range of multipolar charge models for diatomic probes, with applications to interpret Stark spectroscopy measurements in protein active sites. [ABSTRACT FROM AUTHOR]

Vibrational relaxation of CO bound to myoglobin (MbCO) following photoexcitation is investigated using nonequilibrium molecular dynamics (MD) simulations. It is found that harmonic potential energy functions for bond vibrations are not suited to simultaneously and accurately describe vibrational de-excitation and the vibrational spectroscopy of the bound ligand. Only when anharmonic (e.g. Morse) potentials are introduced for both the C−O and the adjacent Fe−CCObonds to allow anharmonic coupling, rapid (tens of ps) relaxation of the vibrationally excited CO is possible. To capture both relaxation and vibrational spectroscopy, the parameters of the potential energy functions are fitted by an interactive, nonlinear least-squares procedure using averages over multiple MD trajectories. The sensitivity of cooling rate to the difference in vibrational frequency between coupled modes is demonstrated. Potential cooling mechanisms are suggested, based on the sensitivity of the CO relaxation rate to changes in the force field parameters of local degrees of freedom. Accounting for quantum correction leads to relaxation rates around 20 ps, in good agreement with experiment. Finally, the importance of electronic effects is explored by fitting a 2D potential energy surface to ab initiodata to describe the strengthening and weakening of the CO bond as a function of Fe−CCObond length, and vice versa. [ABSTRACT FROM AUTHOR]