Erratum: Polarized absorption spectroscopy of Λ-doublet molecules: Transition moment vs electron density distribution [J. Chem. Phys. <b>8</b>
                  <b>7</b>, 5589 (1987)]

Bigio, Laurence; Grant, Edward R.

doi:10.1063/1.455754

Cited by 6 publications

(9 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The R 22 branch transitions probe the ⌸͑AЈ͒ ⌳-doublet state and Q 22 ϩR 12 branch transitions probe the ⌸͑AЉ͒ ⌳-doublet state of NO. 46,48 As shown in Figs. 6͑a͒ and 6͑b͒ there is no difference in the vector correlations of the two ⌳-doublet states within experimental error.…”

Section: B ⌳-Doublet States Of Nomentioning

confidence: 80%

NO μ-v-j correlations in the photofragmentation of 2-chloro-2-nitrosopropane

Uberna

Hinchliffe

Cline

1996

The Journal of Chemical Physics

View full text Add to dashboard Cite

The trajectory of NO X 2 ⌸ ⍀ϭ1/2,3/2 (vϭ0) produced after excitation of 2-chloro-2-nitrosopropane S 1 Ã 1 AЉ is studied by polarized 1ϩ1Ј resonance-enhanced multiphoton ionization with time-of-flight mass spectrometry detection. The correlations among the NO velocity v, angular momentum j, and the S 1 Ã 1 AЉ←S 0 X 1 AЈ ͓n͑N͒,*͑NvO͔͒ transition dipole of the parent molecule are measured. The dissociation occurs by internal conversion to the ground S 0 state or intersystem crossing to the T 1 ã 3 AЉ state and the observed speed distribution of the NO fragments is bimodal. There is no evidence for -v-j correlations for the products associated with the slow component of the speed distribution. For the higher speed component, the v-j correlation is a function of the NO rotational state, j, and is described by the bipolar moment ␤ 0 0 ͑22͒. The average value of ␤ 0 0 ͑22͒ is Ϫ0.17͑Ϯ0.02͒ at jϷ11.5-22.5, more than five times larger than predicted by statistical phase space theory for dissociation on the S 0 X 1 AЈ surface, indicating a moderate preference for a perpendicular orientation of the NO rotational angular momentum and velocity vectors. The v and j vectors are nearly uncorrelated for low NO rotational states ͑jр6.5͒. The -v correlation described by the ␤ 0 2 ͑20͒ bipolar moment does not change with j and its average value is Ϫ0.04͑Ϯ0.01͒ at jϷ12. 5-19.5. The average value of the ␤ 0 2 ͑02͒ bipolar moment describing -j correlation is 0.04͑Ϯ0.02͒ at jϷ7.5-24.5. These results are consistent with a mechanism involving both impulsive force due to a barrier along the reaction coordinate on the T 1 ã 3 AЉ surface and forces resulting from the C-N-O bending and NO torsion about the C-N bond.

show abstract

Section: B ⌳-Doublet States Of Nomentioning

confidence: 80%

NO μ-v-j correlations in the photofragmentation of 2-chloro-2-nitrosopropane

Uberna

Hinchliffe

Cline

1996

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…TheD 2 B 2 state is expected to predissociate within 100 fs [58] via one of two dissociation thresholds, producing either NO( 2 Π) + O( 1 D) (the second dissociation limit at 5.08 eV) or NO( 2 Π) + O( 3 P) (the first dissociation limit at 3.11 eV, see Fig. 9) [27,59]. The production of both NO + and O + due to ionization of free neutral photofragments giving rise to the features observed at <100 fs can be ruled out, since these ion signals rapidly decay after reaching a maximum.…”

Section: B the Role Of Multiphoton Pump Excitation And Relaxation Dymentioning

confidence: 99%

Excited state wavepacket dynamics in NO2 probed by strong-field ionization

Forbes

Boguslavskiy

Wilkinson

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

We present an experimental femtosecond time-resolved study of the 399 nm excited state dynamics of nitrogen dioxide using channel-resolved above threshold ionization (CRATI) as the probe process. This method relies on photoelectron-photoion coincidence and covariance to correlate the strong-field photoelectron spectrum with ionic fragments, which label the channel. In all ionization channels observed, we report apparent oscillations in the ion and photoelectron yields as a function of pump-probe delay. Further, we observe the presence of a persistent, time-invariant above threshold ionization comb in the photoelectron spectra associated with most ionization channels at long time delays. These observations are interpreted in terms of single-pump-photon excitation to the first excited electronic X̃ A state and multi-pump-photon excitations to higher-lying states. The short time delay (<100 fs) dynamics in the fragment channels show multi-photon pump signatures of higher-lying neutral state dynamics, in data sets recorded with higher pump intensities. As expected for pumping NO at 399 nm, non-adiabatic coupling was seen to rapidly re-populate the ground state following excitation to the first excited electronic state, within 200 fs. Subsequent intramolecular vibrational energy redistribution results in the spreading of the ground state vibrational wavepacket into the asymmetric stretch coordinate, allowing the wavepacket to explore nuclear geometries in the asymptotic region of the ground state potential energy surface. Signatures of the vibrationally "hot" ground state wavepacket were observed in the CRATI spectra at longer time delays. This study highlights the complex and sometimes competing phenomena that can arise in strong-field ionization probing of excited state molecular dynamics.

show abstract

“…Phys., 2010, 12, 15766-15779 15777 disagreement with the results of Grant et al who attributed the NO (1) 2 P O fragments of a two photon pump process to the (2) 2 B 2 state resulting in the production of O( 1 D 2 ) atoms. [46][47][48][49] In this case the disparity between the results of Grant et al and those discussed here may be accounted for by differences in the pump laser intensities employed in the different measurements.…”

Section: Atomic Oxygen Fragmentsmentioning

confidence: 55%

“…4.1.1 2 -(1 0 +1 0 ). Two-photon excitation by the pump laser field may populate the (2) 2 B 2 state with resonant enhancement via the (1) 2 B 2 state as proposed by Tsukiyama et al 45 and Grant et al [46][47][48][49] In this case the majority of the population of the short-lived photoexcited state would be expected to decay within 100 fs and neutral NO (1) 2 P O and O( 3 P J ) fragments would be produced. The diatomic fragments could be formed in v = 0-13 and with kinetic energies of between 970 and 0 meV respectively.…”

Section: No + Fragmentsmentioning

confidence: 98%

The photodissociation of NO2 by visible and ultraviolet light

Wilkinson

Garcia

Whitaker

et al. 2010

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We present velocity map images of the NO, O((3)P(J)) and O((1)S(0)) photofragments from NO(2) excited in the range 7.6 to 9.0 eV. The molecule was initially pumped with a visible photon between 2.82-2.95 eV (440-420 nm), below the first dissociation threshold. A second ultraviolet laser with photon energies between 4.77 and 6.05 eV (260-205 nm) was used to pump high-lying excited states of neutral NO(2) and/or probe neutral photoproducts. Analysis of the kinetic energy release spectra revealed that the NO photofragments were predominantly formed in their ground electronic state with little kinetic energy. The O((3)P(J)) and O((1)S(0)) kinetic energy distributions were also dominated by kinetically 'cold' fragments. We discuss the possible excitation schemes and conclude that the unstable photoexcited states probed in the experiment were Rydberg states coupled to dissociative valence states. We compare our results with recent time-resolved studies using similar excitation and probe photon energies.

show abstract

Erratum: Polarized absorption spectroscopy of Λ-doublet molecules: Transition moment vs electron density distribution [J. Chem. Phys. 8 7, 5589 (1987)]

Cited by 6 publications

References 1 publication

NO μ-v-j correlations in the photofragmentation of 2-chloro-2-nitrosopropane

NO μ-v-j correlations in the photofragmentation of 2-chloro-2-nitrosopropane

Excited state wavepacket dynamics in NO2 probed by strong-field ionization

The photodissociation of NO2 by visible and ultraviolet light

Contact Info

Product

Resources

About