Using polarization-selective two-dimensional infrared (2D IR) and infrared pump-probe spectroscopies, we study vibrational relaxation of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O or formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as mod...

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 ...

We present a rigid-ion model of Ba, zK,BiO, for compositions x = 0.25 and x = 0.40. Partial vibrational density ot states of ions in the compounds Ba,, ,? K,, ,,BiO, and Ba,, (,Ki, ,BiO, are reported at room temperature and 100 K. The oxygen modes dominate the vibrational spectrum from 150 up to 82Ocm ‘. The low frequency modes arc associated with the cations. The number of substituted K around...

We present a microscopic description of the vibrational spectroscopy of the OH stretch of HOD in liquid D(2)O. Our model predicts that OH frequency correlations decay with a sharp and rapid ( approximately 35 fs) decrease, followed by a beat at approximately 125 fs from intermolecular oxygen vibrations. On a short time scale ( approximately 200 fs), ultrafast infrared spectroscopy of the OH str...

In the context of molecular quantum computation the optimal control theory (OCT) is used to obtain shaped laser pulses for high-fidelity control of vibrational qubits. Optimization is done in time domain and the OCT algorithm varies values of electric field in each time step independently, tuning hundreds of thousands of parameters to find one optimal solution. Such flexibility is not available...

The influence of solute-solvent interactions on the vibrational energy relaxation dynamics of perylene and substituted perylenes in the first singlet excited-state upon excitation with moderate (<0.4 eV) excess energy has been investigated by monitoring the early narrowing of their fluorescence spectrum. This narrowing was found to occur on timescales ranging from a few hundreds of femtoseconds...

This paper discusses the feasibility of high-frequency nonlinear vibrational control. Such control has the advantage that it does not require state measurement and processing capabilities that are required in conventional feedback control. Bellman et al. [1] investigated nonlinear systems controlled by linear vibrational controllers and proved that vibrational control is not feasible if the Jac...

The terahertz and infrared frequency vibration modes of room-temperature ionic liquids with imidazolium cations and halogen anions were extensively investigated. There is an intermolecular vibrational mode between the imidazolium ring of an imidazolium cation, a halogen atomic anion with a large absorption coefficient and a broad bandwidth in the low THz frequency region (13-130 cm-1), the intr...

The vibrational spectroscopy and relaxation of an anharmonic oscillator coupled to a harmonic bath are examined to assess the applicability of the time correlation function (TCF), the response function, and the semiclassical frequency modulation (SFM) model to the calculation of infrared (IR) spectra. These three approaches are often used in connection with the molecular dynamics simulations bu...

Vibrational spectroscopy is generally implemented using two schemes; that is, absorption spectroscopy and Raman spectroscopy. Conventionally, low frequency absorption spectroscopy is carried out using Fourier transform spectrometers equipped with a far infrared radiation source and a thermal detector. On the other hand, low frequency Raman spectroscopy is carried out by way of double or triple ...