A time-dependent calculation of the alignment and orientation of the CN fragment of the photodissociation of ICN

Carrington, Tucker

doi:10.1063/1.471860

Cited by 22 publications

(16 citation statements)

References 59 publications

(56 reference statements)

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“…See Figure for a schematic picture of the collinear potential curves for the photodissociation. In fact, the distributions of N for each channel have been reproduced by various theoretical calculations . The product CN has the electronic ground state of X 2 Σ + , thus each rotational level N is split in the fine structure levels F 1 ( J = N + 1/2) and F 2 ( J = N − 1/2) due to the spin–rotation interaction (SRI).…”

Section: Introductionmentioning

confidence: 97%

“…The

\overset{A}{true}

‐band ( λ = 210–320 nm) photodissociation of ICN in the gas phase, especially its fragment branching ratios and the stereo dynamics, have suggested the presence of complicated nonadiabatic transitions, and prompted many experimental and theoretical studies over the past 30 years, as described in many reviews and monographs . The following two dissociation channels are known experimentally.

ICN + hν \to \frac{0pt}{normalI ((), {}^{2}{P_{3 / 2}}) + CN ((), X {{}^{2}Σ}^{+} v, N, F_{1} / F_{2})} .

…”

Section: Introductionmentioning

confidence: 99%

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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

et al. 2018

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One of the most spectacular yet unsolved problems for the ICÑ A-band photodissociation is the non-statistical spin-rotation F 1 = N + 1/2 and F 2 = N − 1/2 populations for each rotation level N of the CN fragment. The F 1 /F 2 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 ( 2 P 3/2 ) and I ( 2 P 1/2 ) 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 F 1 and F 2 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 0 and 4A 0 electronic states, and with a four-state model including the 3A 0 through 6A 0 electronic states. These two kinds of interfering models explain general features of the F 1 and F 2 level populations observed by Zare's group and Hall's group, respectively.It is known that the ground state of the I atom has j = 3/2, thus yields the non-zero quadrupole moment due to the non-spherical charge distribution, while the spin-orbit excited state has j = 1/2, WWW.C-CHEM.ORG FULL PAPERWiley Online Library J. Comput. Chem. 2019, 40, 482-499 485 the space-fixed (SF) Z 0 axis is taken as the propagation direction for circularly polarized light (Fig. 2). Then, we focus on the orientation of the SF total angular momentum of photofragment CN. This orientation is defined asHere, J Z 0 M SF J is the space-fixed Z 0 component of the total angular momentum CN, and ρ J ð Þ M SF J M SF J is the relative population observed in the level M SF J and is normalized as P M SF J ρ J ð Þ M SF J M SF J

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Section: Introductionmentioning

confidence: 97%

“…The

\overset{A}{true}

ICN + hν \to \frac{0pt}{normalI ((), {}^{2}{P_{3 / 2}}) + CN ((), X {{}^{2}Σ}^{+} v, N, F_{1} / F_{2})} .

…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2018

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“…The 1 Π 1 (5A') and 3 Π 0+ (4A') states are coupled via a conical intersection after the Franck-Condon region and the bending angle dependence of the surfaces plays an important role in the probability of this curve crossing. These surfaces have been used in classical surface hopping trajectory [23,25], time-independent [26,27] and time-dependent [28,29] quantum scattering calculations.…”

Section: Introductionmentioning

confidence: 99%

Frequency modulated circular dichroism spectroscopy: application to ICN photolysis

et al. 2010

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“…Solving the TDSE enables one to calculate photodissociation cross section, rate constants, etc. [1,2,[7][8][9][10]. Many algorithms have been suggested for solving the TDSE.…”

Section: Introductionmentioning

confidence: 99%

A new approach for determining the time step when propagating with the Lanczos algorithm

Mohankumar¹,

Carrington²

2010

Computer Physics Communications

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A time-dependent calculation of the alignment and orientation of the CN fragment of the photodissociation of ICN

Abstract: Articles you may be interested inQuantum mechanical analysis of photofragment alignment near asymmetric resonances

Cited by 22 publications

References 59 publications

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

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

Frequency modulated circular dichroism spectroscopy: application to ICN photolysis

A new approach for determining the time step when propagating with the Lanczos algorithm

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A time-dependent calculation of the alignment and orientation of the CN fragment of the photodissociation of ICN

Abstract: Articles you may be interested inQuantum mechanical analysis of photofragment alignment near asymmetric resonances

Cited by 22 publications

References 59 publications

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

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

Frequency modulated circular dichroism spectroscopy: application to ICN photolysis

A new approach for determining the time step when propagating with the Lanczos algorithm

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Product

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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

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