A new algorithm for computing anharmonic vibrational states for polyatomic molecules is proposed. The algorithm starts with the vibrational self-consistent field ~VSCF! method and uses degenerate perturbation theory to correct for effects of correlation between different vibrational modes. The algorithm is developed in a version that computes the anharmonic vibrational spectroscopy directly fro...

Linear response functions are implemented for a vibrational configuration interaction state allowing accurate analytical calculations of pure vibrational contributions to dynamical polarizabilities. Sample calculations are presented for the pure vibrational contributions to the polarizabilities of water and formaldehyde. We discuss the convergence of the results with respect to various details ...

The photoelectron spectra of FeO and FeO2 2 are obtained at 3.49 eV photon energy. Transitions to the ground state ~D! and three low-lying excited states ~S, S, and D! of FeO are observed. The two low-spin excited states found at 6770 and 8310 cm above the ground state, respectively, have not been observed before. The two S states, characteristic of detachment of a nonbonding electron from the ...

Although nuclear energy-density functionals are determined primarily by fitting to ground-state properties, they are often applied in nuclear astrophysics to excited states, usually through the quasiparticle random-phase approximation (QRPA). Here we test the Skyrme functionals SkM∗ and SLy4 along with the self-consistent QRPA by calculating properties of low-lying vibrational states in a large...

Electron transport in single-walled carbon nanotubes (SWCNTs) is extremely sensitive to environmental effects. SWCNTs experiencing an inhomogeneous environment are effectively subjected to a disorder potential, which can lead to localized electronic states. An important element of the physical picture of such states localized on the nanometer-scale is the existence of a local vibronic mainfold ...

Vibrational properties of graphene nanoribbons are examined with density functional based tight-binding method and non-resonant bond polarization theory. We show that the recently discovered reconstructed zigzag edge can be identified from the emergence of high-energy vibrational mode due to strong triple bonds at the edges. This mode is visible also in the Raman spectrum. Total vibrational den...

Recent calculations on the formation of self-trapped amide group vibrational states in -helical polypeptides J. Chem. Phys. 124, 134907 2006 are extended to the amide N–H normal mode vibrations. First, the adiabatic N–H vibrational singleand two-exciton states are examined by treating the longitudinal chain coordinates as parameters. Then, in using the multiconfiguration time-dependent Hartree ...

Calculations are discussed which characterize all the vibrational bound states of the H3 and D2H C molecular ions using a realistic ab initio potential energy surface. Graphical analysis and calculation of rotational constants show that both ions support a series of atom–diatom-like long-range states: asymptotic vibrational states. The role of these states in the H3 system and other molecules i...

A model Hamiltonian for photoinduced homogeneous proton-coupled electron transfer reactions is presented, and the equations of motion for the reduced density matrix elements in an electron-proton vibronic basis are derived. This formalism enables a detailed analysis of the proton vibrational dynamics, as well as the dynamics of the electronic state populations, following photoexcitation. The ap...

A potential energy surface is constructed for the ground X (1)A(1) electronic state of cyclic-N(3) (+) based on three-dimensional spline interpolation of ab initio points. The vibrational states of this molecular ion are calculated in the range up to 14 500 cm(-1) using hyperspherical coordinates and the coupled-channel (sector-adiabatic) approach. All the vibrational states are analyzed and as...