Probing Rydberg-Rydberg interactions in N2 by ultrafast EUV-NIR photoelectron spectroscopy
Mizuho Fushitani, Yuto Toida, François Légaré, and Akiyoshi Hishikawa
Mizuho Fushitani,1 Yuto Toida,1 François Légaré,2 and Akiyoshi Hishikawa1,3,*
1Department of Chemistry, Nagoya University, Furo-cho, Chikusa, Nagoya, Aichi 464-8602, Japan
2INRS, Énergie, Matériaux et Télécommunications, 1650 Bld. Lionel Boulet, Varennes, Québec, J3X 1S2, Canada
3Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa, Nagoya, Aichi 464-8602, Japan
*Corresponding author: hishi@chem.nagoya-u.ac.jp
Akiyoshi Hishikawa https://orcid.org/0000-0002-4147-294X
M Fushitani
Y Toida
F Légaré
A Hishikawa
Mizuho Fushitani, Yuto Toida, François Légaré, and Akiyoshi Hishikawa, "Probing Rydberg-Rydberg interactions in N2 by ultrafast EUV-NIR photoelectron spectroscopy," Opt. Express 27, 19702-19711 (2019)
Ultrafast Optics and Attosecond/High-field Physics
Photoelectron spectra
Photoelectron spectroscopy
Radiative processes
Rydberg states
Time resolved spectroscopy
Original Manuscript: April 19, 2019
Revised Manuscript: May 31, 2019
Manuscript Accepted: June 3, 2019
The ultrafast dynamics of molecular nitrogen (N2) just below the ionization threshold has been investigated by time-resolved photoelectron spectroscopy using a single harmonic centered at hν = 15.38 eV. The evolution of the Rydberg wavepacket launched by the ultrashort EUV pulse is probed by a time-delayed femtosecond NIR laser pulse. The observed photoelectron spectra show two series of vibrational peaks to the ground X2Σg+ state and the first excited A2Πu state of N2+. Among these, two photoelectron peaks with the vibrational quantum numbers vX+ = 4 and vA+ = 1 exhibit clear anti-phase oscillation with a period of 300 fs, showing that two Rydberg states converging to the X2Σg+ and A2Πu ionic states interact with each other, thus causing periodic switching in the population of the ion core states.
Time-resolved EUV photoelectron spectroscopy of dissociating I2 by laser harmonics at 80 nm
Mizuho Fushitani, Akitaka Matsuda, and Akiyoshi Hishikawa
Opt. Express 19(10) 9600-9606 (2011)
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Annu. Rev. Phys. Chem. (1)
Faraday Discuss. (1)
J. Chem. Phys. (6)
J. Electron Spectrosc. Relat. Phenom. (1)
J. Phys. B: At. Mol. Opt. Phys. (3)
J. Phys. Chem. A (2)
Phys. Rev. A (2)
Sci. Adv. (1)
Struct. Dyn. (1)
Fig. 1 (a) Potential energy curves of the Rydberg states of N2 converging to the X 2 Σ g + and A2Πu states and ionic states in N 2 + [23, 24]. An ultrashort EUV pump pulse (15.38 eV) creates the molecular Rydberg wavepacket. The evolution is probed by an NIR pulse introduced with a time delay of Δt. The photoelectron spectroscopy is employed to study the interaction between the Rydberg states. (b) Oscillator strengths of Rydberg states of N2 in the range between 15.36 and 15.40 eV [27,28]. These Rydberg states form two main bands around 15.386 and 15.373 eV.
Fig. 2 (a) EUV-NIR photoelectron spectrogram of Rydberg N2 plotted with the pump-probe time delay Δt and the photoelectron energy. Shown on the bottom is the photoelectron spectrum recorded at Δt = 1000 fs. The peak assignments are shown on the top. (b) Time-evolution of the photoelectron intensities for the vX+ = 0–4, vA+ = 1 peaks.
Fig. 3 Fourier-transform of the observed time-resolved photoelectron spectrogram as a function of the photoelectron energy. Solid lines indicate the differences in the state energies between the A+(1)3dδ Rydberg state and other Rydberg states in the energy range excited by the EUV pulses.
Fig. 4 (a) Energy level diagram of the X+(4)4pπ and A+(1)3dδ Rydberg states. The unperturbed levels have energies of 124076 and 124033 cm−1 from the ground state with the difference of ΔE(0) = 43 cm−1, which are estimated [27] from the corresponding Rydberg series. By the perturbation, the eigenstates, ψ+ and ψ−, assigned to the X+(4)4pπ and A+(1)3dδ Rydberg states, respectively, are formed to have the energy difference of ΔE = 110 cm−1 [27]. The coherent superposition of these eigenstates results in the periodic oscillation of the intensities of the vX+ = 4 and vA+ = 1 photoelectron peaks. (b) Highest occupied molecular orbital (HOMO) and HOMO-1 of the N 2 + core, 3σg and 1πg.
(1) Ψ ( t ) = a + ψ + exp ( − i E + t ) + a − ψ − exp ( − i E − t ) ,
(2) c 1 = [ Δ E + Δ E ( 0 ) 2 Δ E ] 1 / 2 , c 2 = ± [ Δ E − Δ E ( 0 ) 2 Δ E ] 1 / 2
(3) Ψ ( t ) = [ a + c 1 exp ( − i E + t ) + a − c 2 exp ( − i E − t ) ] | X + ( 4 ) 4 p π 〉 + [ a + c 2 exp ( − i E + t ) − a − c 1 exp ( − i E − t ) ] | A + ( 1 ) 3 d δ 〉 ,
(4) I X + ( 4 ) ( t ) ~ | 〈 ∊ | μ | 4 p π 〉 | 2 [ a + 2 c 1 2 + a − 2 c 2 2 + 2 a + a − c 1 c 2 cos ( Δ E t ) ] I A + ( 1 ) ( t ) ~ | 〈 ∊ | μ | 3 d δ 〉 | 2 [ a − 2 c 1 2 + a + 2 c 2 2 − 2 a + a − c 1 c 2 cos ( Δ E t ) ] ,