The time-resolved photoelectron spectrum of toluene using a perturbation theory approach

Journal Article · Sun Dec 28 00:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4904079· OSTI ID:22415412

Richings, Gareth W.

A theoretical study of the intra-molecular vibrational-energy redistribution of toluene using time-resolved photo-electron spectra calculated using nuclear quantum dynamics and a simple, two-mode model is presented. Calculations have been carried out using the multi-configuration time-dependent Hartree method, using three levels of approximation for the calculation of the spectra. The first is a full quantum dynamics simulation with a discretisation of the continuum wavefunction of the ejected electron, whilst the second uses first-order perturbation theory to calculate the wavefunction of the ion. Both methods rely on the explicit inclusion of both the pump and probe laser pulses. The third method includes only the pump pulse and generates the photo-electron spectrum by projection of the pumped wavepacket onto the ion potential energy surface, followed by evaluation of the Fourier transform of the autocorrelation function of the subsequently propagated wavepacket. The calculations performed have been used to study the periodic population flow between the 6a and 10b16b modes in the S{sub 1} excited state, and compared to recent experimental data. We obtain results in excellent agreement with the experiment and note the efficiency of the perturbation method.

• OSTI ID: 22415412
• Journal Information: Journal of Chemical Physics, Vol. 141, Issue 24; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
APPROXIMATIONS
COMPARATIVE EVALUATIONS
ELECTRON SPECTRA
ELECTRONS
EXCITED STATES
FOURIER TRANSFORMATION
LASER RADIATION
PERIODICITY
PERTURBATION THEORY
PHOTOELECTRON SPECTROSCOPY
POTENTIAL ENERGY
SURFACES
TIME DEPENDENCE
TIME RESOLUTION
TOLUENE
WAVE FUNCTIONS
WAVE PACKETS