Torsional Wave-Packet Dynamics in 2-Fluorobiphenyl Investigated by State-Selective Ionization-Detected Impulsive Stimulated Raman Spectroscopy

Abstract

We report the creation and observation of vibrational wave packets pertinent to torsional motion in a biphenyl derivative in its electronic ground-state manifold. Adiabatically cooled molecular samples of 2-fluorobiphenyl were irradiated by intense nonresonant ultrashort laser pulses to drive impulsive stimulated Raman excitation of torsional motion. Spectral change due to the nonadiabatic vibrational excitation is probed in a state-selective manner using resonance-enhanced two-photon ionization through the S1 ← S0 electronic transition. The coherent nature of the excitation was exemplified by adopting irradiation with a pair of pump pulses: observed signals for excited torsional levels exhibit oscillatory variations against the mutual delay between the pump pulses due to wave-packet interference. By taking the Fourier transform of the time course of the signals, energy intervals among torsional levels with v = 0–3 were determined and utilized to calibrate a density functional theory (DFT)-calculated torsional potential-energy function. Time variation of populations in the excited torsional levels was assessed experimentally by measuring integrated intensities of the corresponding transitions while scanning the delay. Early time enhancement of the population (up to ∼2 ps) and gradual degradation of coherence (within ∼20 ps) appears. To explain the observed distinctive features, we developed a four-dimensional (4D) dynamical calculation in which one-dimensional (1D) quantum-mechanical propagation of the torsional motion was followed by solving the time-dependent Schrödinger equation, whereas three-dimensional (3D) molecular rotation was tracked by classical trajectory calculations. This hybrid approach enabled us to reproduce experimental results at a reasonable computational cost and provided a deeper insight into rotational effects on vibrational wave-packet dynamics.

Two-Dimensional Infrared Spectroscopy of Isolated Molecular Ions

“…The application of ultrafast pulses also presents the challenge of how to frequency resolve an action response with a broadband source. Seminal work by Marcus, − Brixner, , Stienkemeier, , and others − have established the ability of indirect action responses, such as fluorescence, ionization, and photofragmentation, to encode nonlinear molecular responses. These responses can be frequency-resolved from time-domain measurements collected using a series of pulses.…”

Two-Dimensional Infrared Spectroscopy of Isolated Molecular Ions

“…The application of ultrafast pulses also presents the challenge of how to frequency resolve an action response with a broadband source. Seminal work by Marcus, [27][28][29] Brixner, [30][31][32] Stienkemeier, [33][34][35] and others [36][37][38][39] have established the ability of indirect action responses such as fluorescence, ionization, and photofragmentation to encode nonlinear molecular responses. These responses can be frequency resolved from time-domain measurements collected using a series of pulses.…”