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The Journal of Chemical Physics

Coherent population transfer in molecules coupled with a dissipative environment by an intense ultrashort chirped pulse

Boris D. Fainberg, Vladimir A. Gorbunov

Published Oct 7, 2002• 34 citations
Publisher

Abstract

We have studied the intense chirped pulse excitation of a molecule coupled with a dissipative environment taking into account electronic coherence effects. We considered a two-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. This relaxation model enables us to trace continuously the transition from a coherent population transfer to incoherent one. An inhomogeneously broadened system with frozen nuclear motion is invoked to model a purely coherent transfer. We show that the type of population transfer (coherent or incoherent) strongly depends on the pulse chirp, its sign, and the detunings of the exciting pulse carrier frequency with respect to the frequency of the Franck-Condon transition. For positive chirped pulses and moderate detunings, relaxation does not hinder a coherent population transfer. Moreover, under these conditions the relaxation favors more efficient population transfer with respect to the “coherent” system with frozen nuclear motion.

DOI
10.1063/1.1505869

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We have studied the intense chirped pulse excitation of a molecule coupled with a dissipative environment taking into account electronic coherence effects. We considered a two-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. This relaxation model enables us to trace continuously the transition from a coherent population transfer to incoherent one. An inhomogeneously broadened system with frozen nuclear motion is invoked to model a purely coherent transfer. We show that the type of population transfer (coherent or incoherent) strongly depends on the pulse chirp, its sign, and the detunings of the exciting pulse carrier frequency with respect to the frequency of the Franck-Condon transition. For positive chirped pulses and moderate detunings, relaxation does not hinder a coherent population transfer. Moreover, under these conditions the relaxation favors more efficient population transfer with respect to the “coherent” system with frozen nuclear motion.
Summary form only given. The effect of relaxation processes on a coherent excitation of a molecule coupled with a dissipative environment is an intriguing question. The purpose of this work is to answer the following question: How does dissipative environment influence on a coherent excitation of a molecule? We have studied the influence of the chirp rate on the excited state population after the completion of pulse action. We used a model of Gaussian-Markovian modulation for description of relaxation processes.
We have developed a simple and physically clear picture of adiabatic rapid passage (ARP) in molecules in solution by careful examination of all the conditions needed for ARP. The relaxation effects were considered in the framework of the Landau-Zener model for random crossing of levels. The model enables us to include into consideration non-Markovian Gaussian-correlated noise. It explains all the numerical results obtained in the first paper of the series [B. D. Fainberg and V. A. Gorbunov, J. Chem. Phys. 117, 7222 (2002)], in particular, that for positive chirp pulse excitation relaxation favors more efficient population transfer with respect to the relaxation-free system with frozen nuclear motion. We also relate parameters of non-Markovian Gaussian-correlated noise with irreversible dephasing time of an optical transition by calculating the photon echo signal attenuation.
We discuss electronic population transfer in diatomic molecules. By analyzing time-dependent wave packets on electronic potential-energy surfaces, we investigate the efficiency and robustness of population transfer with intense, chirped laser pulses. Recently, the magnitude of the population transfer was observed to have a remarkable dependence on the sign of the chirp [J. Cao, C. J. Bardeen, and K. R. Wilson, Phys. Rev. Lett. 80, 1406 (1998)]. In this work we explain the reason for this asymmetry, and show how the frequency detuning, intensity, and chirp rate affect the results. In particular, we demonstrate efficient, robust population transfer for both positive and negative chirps. A Landau-Zener model of multiple avoided crossings is invoked to model the results.
The influence of excited-state absorption (ESA) and two-exciton processes on a coherent population transfer with intense ultrashort chirped pulses in molecular systems in solution has been studied. A unified treatment of adiabatic rapid passage (ARP) in such systems has been developed using a three-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. We have shown that ESA has a profound effect on coherent population transfer in large molecules that necessitates a more accurate interpretation of experimental data. A simple and physically clear model for ARP in molecules with three electronic states in solution has been developed by extending the Landau-Zener calculations putting in a third level to random crossing of levels. A method for quantum control of two-exciton states in molecular complexes has been proposed. 1.
A coherent control scheme for the population distribution in the vibrational states of nonpolar molecules is proposed. Our theoretical analysis and results of numerical simulations for the interaction of the hydrogen molecular ion in its electronic ground state with an infrared laser pulse reveal a selective two-photon transition between the vibrational states via a coupling with the first excited dissociative state. We demonstrate that for a given temporal intensity profile the population transfer between vibrational states, or a superposition of vibrational states, can be made complete for a single chirped pulse or a train of chirped pulses, which accounts for the accumulated phase difference due to the ac Stark effect. Effects of a spatial intensity (or focal) averaging are discussed.
Detailed theoretical analysis and numerical simulation indicate that nearly complete electronic population inversion of molecular systems can be achieved with intense positively chirped broadband laser pulses. To provide a simple physical picture, a two-level model is used to examine the condition for the so-called π pulses and a four-level model is designed to demonstrate for molecular systems the correlation between the sign of the chirp and the excited state population. The proposed molecular π pulse is the combined result of vibrational coherence in the femtosecond regime and adiabatic inversion in the picosecond regime. Numerical results for a displaced oscillator, for LiH and for I2, show that the proposed molecular π pulse scheme is robust with respect to changes in field parameters such as the linear positive chirp rate, field intensity, bandwidth, and carrier frequency, and is stable with respect to thermal and condensed phase conditions including molecular rotation, rovibronic coupling, and electronic dephasing.