Infrared-pump–x-ray-probe spectroscopy of vibrationally excited molecules
Nenhuma Miniatura disponível
Data
2017
Título da Revista
ISSN da Revista
Título de Volume
Editor
Resumo
We develop a theory of infrared (IR)-pump–x-ray-probe spectroscopy for molecular studies. We illustrate
advantages of the proposed scheme by means of numerical simulations employing a vibrational wave packet
technique applied to x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectra of the water
molecule vibrationally excited by a preceding IR field. The promotion of the vibrationally excited molecule
to the dissociative 1a−1
1 4a1 and bound 1a−1
1 2b2 core-excited states with qualitatively different shapes of the
potential energy surfaces creates nuclear wave packets localized along and between the OH bonds, respectively.
The projection of these wave packets on the final vibrational states, governed by selection and propensity rules,
results in spatial selectivity of RIXS sensitive to the initial vibrationally excited state, which makes it possible
to probe selectively the ground state properties along different modes. In addition, we propose to use RIXS
as a tool to study x-ray absorption from a selected vibrational level of the ground state when the spectral
resolution is sufficiently high to resolve vibrational overtones. The proposed technique has potential applications
for advanced mapping of multidimensional potential energy surfaces of ground and core-excited molecular states,
for symmetry-resolved spectroscopy, and for steering chemical reactions.
Descrição
Palavras-chave
Citação
IGNATOVA, Nina et al. Infrared-pump-x-ray-probe spectroscopy of vibrationally excited molecules. Physical Review A, [s. l.], v. 95, n. 4, e042502, 2017. DOI: 10.1103/PhysRevA.95.042502. Disponível em: https://journals.aps.org/pra/abstract/10.1103/PhysRevA.95.042502. Acesso em: 13 dez. 2023.