Potential energy surfaces and nonadiabatic transitions in the asymptotic regions of ICN photodissociation to study the interference effects in the F1 and F2 spin-rotation levels of the CN products

Tatsuhiko Kashimura, Tomoya Ikezaki, Yusuke Ohta, Satoshi Yabushita

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Abstract

One of the most spectacular yet unsolved problems for the ICN (Formula presented.) -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N. We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's grousp and Hall's group, respectively.

Original languageEnglish
Pages (from-to)482-499
Number of pages18
JournalJournal of Computational Chemistry
Volume40
Issue number2
DOIs
Publication statusPublished - 2019 Jan 15

Fingerprint

Photodissociation
Potential Energy Surface
Potential energy surfaces
Interference
Electronic states
Electronics
Switch
Fragment
Switches
Hamiltonians
Open Channel
Exchange Interaction
Exchange interactions
Wave functions
Interaction
Dipole
Quantization
Model
Symmetry

Keywords

  • dipole-quadrupole interactions
  • F and F spin-rotation levels
  • fine structure splitting
  • interference effect
  • Rosen-Zener-Demkov nonadiabatic transitions

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

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title = "Potential energy surfaces and nonadiabatic transitions in the asymptotic regions of ICN photodissociation to study the interference effects in the F1 and F2 spin-rotation levels of the CN products",
abstract = "One of the most spectacular yet unsolved problems for the ICN (Formula presented.) -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N. We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's grousp and Hall's group, respectively.",
keywords = "dipole-quadrupole interactions, F and F spin-rotation levels, fine structure splitting, interference effect, Rosen-Zener-Demkov nonadiabatic transitions",
author = "Tatsuhiko Kashimura and Tomoya Ikezaki and Yusuke Ohta and Satoshi Yabushita",
year = "2019",
month = "1",
day = "15",
doi = "10.1002/jcc.25736",
language = "English",
volume = "40",
pages = "482--499",
journal = "Journal of Computational Chemistry",
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TY - JOUR

T1 - Potential energy surfaces and nonadiabatic transitions in the asymptotic regions of ICN photodissociation to study the interference effects in the F1 and F2 spin-rotation levels of the CN products

AU - Kashimura, Tatsuhiko

AU - Ikezaki, Tomoya

AU - Ohta, Yusuke

AU - Yabushita, Satoshi

PY - 2019/1/15

Y1 - 2019/1/15

N2 - One of the most spectacular yet unsolved problems for the ICN (Formula presented.) -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N. We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's grousp and Hall's group, respectively.

AB - One of the most spectacular yet unsolved problems for the ICN (Formula presented.) -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N. We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's grousp and Hall's group, respectively.

KW - dipole-quadrupole interactions

KW - F and F spin-rotation levels

KW - fine structure splitting

KW - interference effect

KW - Rosen-Zener-Demkov nonadiabatic transitions

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U2 - 10.1002/jcc.25736

DO - 10.1002/jcc.25736

M3 - Article

VL - 40

SP - 482

EP - 499

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

SN - 0192-8651

IS - 2

ER -