Coherent Quantum Control of Multidimensional Vibrational Spectroscopy
Abstract
The difference frequency generation (DFG) signal from a two electronic level system with vibrational modes coupled to a Brownian oscillator bath was computed. Simulations of two-dimensional DFG signals illustrated how the ground and excited electronic state resonances may be distinguished. Factorial moments of photon counting statistics from a single molecule coupled to a quantum bath were expressed in terms of multipoint quantum correlation functions and represented by double-sided Feynman diagrams. The results of stochastic models of spectral diffusion where the bath dynamics were independent of the state of the system were recovered and the moments described. Closed expressions for tunneling currents in molecular junctions were derived in electron-phonon coupling. The Keldysh-Schwinger formalism was recast in terms of density matrices in Liouville space. The current was related to the decay of coherences in Fock space between many-body molecular states. Effects of hydrogen-bond forming and breaking kinetics on the linear and coherent third-order infrared spectra were described by Markovian fluctuations and simulated using stochastic Liouville equations. Slow and fast frequency fluctuations were distinguished and described. Recursive relations were developed for computing the multipoint correlation functions of a particle undergoing a biased continuous-time random walk (CTRW) in an external potential. Comparison of the CTRW with the Brownian harmonic oscillator model illustrated how higher-order correlation functions may be used to distinguish between dynamical models that have the same two-point correlation function.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 01, 2006
- Accession Number
- ADA450362
Entities
People
- Dmitri Varonine
- Frantisek Sanda
- Ravi Venkatramani
- Shaul Mukamel
- Upendra Harbola
Organizations
- University of California, Irvine