Vibrational eigenvalues and eigenfunctions for planar acetylene by wave-packet propagation, and its mode-selective infrared excitation

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Abstract

Vibrational eigenvalues with estimated errors -2 cm-1 and their corresponding eigenfunctions for J=0 5D (planar) acetylene modeled by the Halonen-Child-Carter potential-energy surface are obtained using an energy-shifted, imaginary-time Lanczos propagation of symmetry-adapted wave packets. A lower resolution (∼4 cm-1) vibrational eigenspectrum of the system is also calculated by the Fourier transform of the autocorrelation of an appropriate wave packet. The eigenvalues from both approaches are in excellent agreement. The wave function of the molecule is represented in a direct-product discrete variable representation (DVR) with nearly 300000 grid points. Our results are compared with the previously reported theoretical and experimental values. We use our 69 computed eigenstates as a basis to perform an optimal control simulation of selective two-photon excitation of the symmetric CH-stretch mode with an infrared, linearly polarized, transform-limited, and subpicosecond-picosecond laser pulse. The resulting optimal laser pulses, which are then tested on the full DVR grid, fall within the capabilities of current powerful, subpicosecond, and tunable light sources.

Original languageEnglish
Pages (from-to)3402-3416
Number of pages15
JournalJournal of Chemical Physics
Volume107
Issue number9
Publication statusPublished - Sep 1 1997

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Wave packets
Acetylene
Eigenvalues and eigenfunctions
acetylene
wave packets
Laser pulses
eigenvectors
eigenvalues
grids
control simulation
Infrared radiation
Potential energy surfaces
propagation
optimal control
Wave functions
pulses
Autocorrelation
autocorrelation
excitation
lasers

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "Vibrational eigenvalues with estimated errors -2 cm-1 and their corresponding eigenfunctions for J=0 5D (planar) acetylene modeled by the Halonen-Child-Carter potential-energy surface are obtained using an energy-shifted, imaginary-time Lanczos propagation of symmetry-adapted wave packets. A lower resolution (∼4 cm-1) vibrational eigenspectrum of the system is also calculated by the Fourier transform of the autocorrelation of an appropriate wave packet. The eigenvalues from both approaches are in excellent agreement. The wave function of the molecule is represented in a direct-product discrete variable representation (DVR) with nearly 300000 grid points. Our results are compared with the previously reported theoretical and experimental values. We use our 69 computed eigenstates as a basis to perform an optimal control simulation of selective two-photon excitation of the symmetric CH-stretch mode with an infrared, linearly polarized, transform-limited, and subpicosecond-picosecond laser pulse. The resulting optimal laser pulses, which are then tested on the full DVR grid, fall within the capabilities of current powerful, subpicosecond, and tunable light sources.",
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N2 - Vibrational eigenvalues with estimated errors -2 cm-1 and their corresponding eigenfunctions for J=0 5D (planar) acetylene modeled by the Halonen-Child-Carter potential-energy surface are obtained using an energy-shifted, imaginary-time Lanczos propagation of symmetry-adapted wave packets. A lower resolution (∼4 cm-1) vibrational eigenspectrum of the system is also calculated by the Fourier transform of the autocorrelation of an appropriate wave packet. The eigenvalues from both approaches are in excellent agreement. The wave function of the molecule is represented in a direct-product discrete variable representation (DVR) with nearly 300000 grid points. Our results are compared with the previously reported theoretical and experimental values. We use our 69 computed eigenstates as a basis to perform an optimal control simulation of selective two-photon excitation of the symmetric CH-stretch mode with an infrared, linearly polarized, transform-limited, and subpicosecond-picosecond laser pulse. The resulting optimal laser pulses, which are then tested on the full DVR grid, fall within the capabilities of current powerful, subpicosecond, and tunable light sources.

AB - Vibrational eigenvalues with estimated errors -2 cm-1 and their corresponding eigenfunctions for J=0 5D (planar) acetylene modeled by the Halonen-Child-Carter potential-energy surface are obtained using an energy-shifted, imaginary-time Lanczos propagation of symmetry-adapted wave packets. A lower resolution (∼4 cm-1) vibrational eigenspectrum of the system is also calculated by the Fourier transform of the autocorrelation of an appropriate wave packet. The eigenvalues from both approaches are in excellent agreement. The wave function of the molecule is represented in a direct-product discrete variable representation (DVR) with nearly 300000 grid points. Our results are compared with the previously reported theoretical and experimental values. We use our 69 computed eigenstates as a basis to perform an optimal control simulation of selective two-photon excitation of the symmetric CH-stretch mode with an infrared, linearly polarized, transform-limited, and subpicosecond-picosecond laser pulse. The resulting optimal laser pulses, which are then tested on the full DVR grid, fall within the capabilities of current powerful, subpicosecond, and tunable light sources.

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