A characterization of vibrationally and electronically excited NO2+ by high-resolution threshold photoionization spectroscopy

Jarvis, G. K.; Song, Yang; Ng, C. Y.; Grant, Edward R.

doi:10.1063/1.480288

Cited by 29 publications

(75 citation statements)

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“…In the next section we mention the previous MRCI T 0 values [21] and the experimental T 0 values from ref. [19].…”

Section: Statementioning

confidence: 95%

“…Among these calculated states we identified the eight states that correspond to the eight ionic states below 20 eV observed in the photoelectron spectra. [1,2] On the basis of our calculation results, we will comment on the state assignments presented in the experimental paper of Jarvis et al [19] and on some of the MRCI results presented in the previous theoretical paper of Hirst. [21] The CASPT2 and CASSCF methods were also used for a theoretical study of O-loss photodissociation from the five low-…”

mentioning

confidence: 93%

“…In their threshold photoionization spectrum of NO 2 , Jarvis et al [19] [4][5][6][7][8][9][10][11][12][13][14][15][16] The researchers detected many dissociation products, thus indicating many dissociation channels, and they were also interested in the branching ratios of different dissociation channels and the dissociation rates in different states of NO 2 + . Herein, we study only O-loss photodissociation in low-lying states of NO 2 + (we will not study branching ratios of dissociation and dissociation rates).…”

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confidence: 99%

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A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion

Chang

Huang

2009

ChemPhysChem

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CASPT2 (multiconfiguration second-order perturbation theory) calculations were performed at the molecular geometry for 17 low-lying singlet and triplet states of the NO(2)(+) ion. The CASPT2 vertical relative energies (T(v)') were obtained and the characters of these ionic states (primary or shake-up ionization states) were determined. For the eight low-lying states, we performed CASPT2 geometry optimization calculations and obtained the CASPT2 adiabatic relative energies (T(0)). We conclude that the 1(1)A(1), 1(3)B(2), 1(3)A(2), 1(1)A(2), 1(1)B(2), 1(3)A(1), 2(3)B(1), and 3(3)B(2) states of NO(2)(+) correspond to the X(1)Sigma(g)(+), a(3)B(2), b(3)A(2), A(1)A(2), B(1)B(2), c(3)A(1), d(3)B(1), and (3b(2))(-1) (3)B(2) states (the eight ionic states below 20 eV observed in the photoelectron spectra of Brundle et al.1 and Baltzer et al.2), respectively. The 1(1)A(1), 1(3)B(2), 1(3)A(2), 1(1)A(2), 1(1)B(2), 1(3)A(1), and 3(3)B(2) states are primary ionization states, and the CASPT2 T(v)' and T(0) values of these states are close to the corresponding experimental values from refs. [1] and [2]. The 2(3)B(1) state is not a typical primary ionization state, and the CASPT2 T(v)' and T(0) values for 2(3)B(1) are in reasonable agreement with the experimental values for d(3)B(1) from refs. [1] and [2] (the CASPT2 T(0) value for 1(3)B(1) is more than 2.5 eV smaller than the experimental values). Based on our CASPT2 T(0) calculations, we comment on the assignments of the d(3)A(1), C(1)B(1), and D(1)B(2) states below 20 eV observed by Jarvis et al. and on the MRCI T(0) values of Hirst for the 1(3)B(1), 1(1)B(1), and (3)A(1) states. On the basis of the CASPT2 potential energy curve (PEC) and CASSCF singlet/triplet minimum-energy crossing point (MECP) calculations, we reach the following conclusions concerning O-loss photodissociation from the X(1)Sigma(g)(+), a(3)B(2), b(3)A(2), A(1)A(2), and B(1)B(2) states, which are in line with the experimental facts. The adiabatic dissociation process of the X(1)Sigma(g) (+) state to the second limit [NO(+)(X(1)Sigma(+))+O((1)D)] cannot occur due to a high energy barrier (>5.0 eV) along the PEC, and the nonadiabitic process of X(1)Sigma(g)(+) to the first limit [NO(+)(X(1)Sigma(+))+O((3)P)] via the triplet states is unlikely since the MECPs lie very high above X(1)Sigma(g)(+). For the a(3)B(2) and b(3)A(2) states, adiabatic dissociation processes to the first limit may occur. Both the A(1)A(2) and B(1)B(2) states can undergo processes of predissociation to the first limit by a repulsive 2(3)A'' state, since the MECPs lie low above A(1)A(2) and B(1)B(2) and the calculated spin-orbit couplings at the MECPs are not small.

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“…In the next section we mention the previous MRCI T 0 values [21] and the experimental T 0 values from ref. [19].…”

Section: Statementioning

confidence: 95%

mentioning

confidence: 93%

mentioning

confidence: 99%

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A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion

Chang

Huang

2009

ChemPhysChem

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“…[35][36][37] The ground state of the cation is linear, and ionization from the bent neutral ground state results in a long vibrational progression. The first excited state of the ion, 3 AЈ ͑or 3 B 2 in C 2v notation͒, is bent at its equilibrium geometry.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO2

Arasaki

Takatsuka²,

Wang³

et al. 2010

The Journal of Chemical Physics

104

111

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We report the results of theoretical studies of the time-resolved femtosecond photoelectron spectroscopy of quantum wavepackets through the conical intersection between the first two 2 AЈ states of NO 2 . The Hamiltonian explicitly includes the pump-pulse interaction, the nonadiabatic coupling due to the conical intersection between the neutral states, and the probe interaction between the neutral states and discretized photoelectron continua. Geometry-and energy-dependent photoionization matrix elements are explicitly incorporated in these studies. Photoelectron angular distributions are seen to provide a clearer picture of the ionization channels and underlying wavepacket dynamics around the conical intersection than energy-resolved spectra. Time-resolved photoelectron velocity map images are also presented.

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“…[14][15][16][17][18][19] The femtosecond time-resolved photoelectron-photoion coincidence imaging technique was pioneered by Hayden and co-workers and applied to NO 2 , 20,21 CF 3 I, 22 and the NO dimer. 23 In particular, Hayden and co-workers studied the femtosecond dynamics of NO 2 in a single color pump-probe experiment at 375 nm.…”

Section: Introductionmentioning

confidence: 99%

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

Vredenborg¹,

Roeterdink²,

Janssen³

2008

The Journal of Chemical Physics

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The multiphoton multichannel photodynamics of NO 2 has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO 2 photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO 2 + parent ions and NO + fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO 2 + or NO + and the ͑NO + , e͒ photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A 2 B 2 state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO 2 + parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO 2 + parent ion. Slow statistical and fast direct fragmentation of NO 2 + after prompt photoelectron ejection is observed leading to formation of NO + + O. Fragmentation from both the ground state and the electronically excited a 3 B 2 and b 3 A 2 states of NO 2 + is observed. At short pump probe delay times, the dominant multiphoton pathway for NO + formation is a 3 ϫ 400 nm+ 1 ϫ 266 nm excitation. At long delay times ͑Ͼ500 fs͒ two multiphoton pathways are observed. The dominant pathway is a 1 ϫ 400 nm+ 2 ϫ 266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3 ϫ 400 nm photon absorption to NO 2 Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO͑A 2 ⌺ , v =1͒ fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO 2 . We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.

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A characterization of vibrationally and electronically excited NO2+ by high-resolution threshold photoionization spectroscopy

Cited by 29 publications

References 27 publications

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion

Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO2

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

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A characterization of vibrationally and electronically excited NO2+ by high-resolution threshold photoionization spectroscopy

Cited by 29 publications

References 27 publications

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO2+ Ion

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO2+ Ion

Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO2

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

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A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion

A Theoretical Study on the Electronic States and O‐Loss Photodissociation of the NO₂⁺ Ion