Spatially localized vibrational normal mode coordinates are shown to reduce the importance of calculating full set two-electron terms in molecular electronic Schrödinger equation. Electron correlation and dispersion interactions become less significant (E,E)-1,3,5,7-octatetraene self-consistent field calculations when displacing remote atoms along multiple coordinates. between spatially modes a...

We study the vibrational energy relaxation (VER) and collisional dephasing as channels of coherence loss in a vibrational mode that is selectively excited using chirped pulse adiabatic passage in the Raman configuration. Based on the dressed state picture analysis we propose a method to reduce decoherence using femtosecond chirped pulse trains. When applied with a period close to the VER time, ...

The 351 .l-nm photoelectron spectra of HFC=C:and F2C=C:are reported. Transitions from the anion ground state to the neutral singlet ground state and low-lying triplet states are observed. The electron affinity of difluorovinylidene is 2.255 (6) eV, and the triplet term energy is To(H 3A2 F,CC) = 0.924 (9) eV. In the singlet state of F2C=C:, vibrational progressions are observed at 510 (25), 905...

The first goal of vibration-transit (V-T) theory was to construct a tractable approximate Hamiltonian from which the equilibrium thermodynamic properties of monatomic liquids can be calculated. The Hamiltonian for vibrations in an infinitely extended harmonic random valley, together with the universal multiplicity of such valleys, gives an accurate first-principles account of the measured therm...

We have recorded several rovibronic bands of CH3OO and CD3OO in their A<--X transitions in the range of 1.18-1.40 microm with the cavity ringdown technique. While the electronic origins for these species have been reported previously, many newly observed rovibronic bands are described here. The experimental vibrational frequencies (given as nu in the unit cm(-1) in this paper) for the COO bendi...

Vibronically resolved S1 ↔ S0 electronic spectra of a doubly hydrogen-bonded mixed dimer between acetic acid and 3-fluorobenzoic acid have been investigated by measuring laser-induced fluorescence excitation and dispersed fluorescence spectra in a cold supersonic jet expansion. Two isomeric species of the dimer have been identified, and the measurements show that their vibronic spectral pattern...

We study the vibrational decoherence dynamics of an iodine molecule in a finite krypton cluster comprising the first solvation shell. A normal mode analysis allows us to successively increase the complexity of the description. For the ground state dynamics, comparison with experimental matrix results shows that already four degrees of freedom are sufficient to capture the main decoherence mecha...

We study the vibrational decoherence dynamics of an iodine molecule in a finite krypton cluster comprising the first solvation shell. A normal mode analysis allows us to successively increase the complexity of the description. For the ground state dynamics, comparison with experimental matrix results shows that already four degrees of freedom are sufficient to capture the main decoherence mecha...

Pure amorphous solids are traditionally considered to set the lower bound of thermal conductivity due to their disordered atomic structure that impedes vibrational energy transport. However, the lower limits for thermal conductivity in heterogeneous amorphous solids and the physical mechanisms underlying these limits remain unclear. Here, we use equilibrium molecular dynamics to show that an am...

[1] The vibrational properties of Mg2SiO4 wadsleyite have been calculated over a wide pressure range using density functional perturbation theory (DFPT). Both the normal mode frequencies and their volume dependences are consistent with the available Raman and infrared data. We provide detailed information about vibrational properties that are still not experimentally available. The vibrational ...