Subfemtosecond Quantum Nuclear Dynamics in Water Isotopomers

Rao, B. Jayachander; Varandas, A. J. C.

doi:10.1021/acs.jpca.5b02129

Cited by 7 publications

(18 citation statements)

References 44 publications

(118 reference statements)

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“…This finding can be explained by the difference in masses between deuterium and proton, which results in different bond stretching frequencies when they are allowed to move on the same repulsive potential. Previous investigations − on the photodissociation of HOD on its first excited-state PES gave similar results. It is important to mention that classical trajectory calculations on HOD 2+ gave the value of branching ratio 8.6, which is quite different from quantum results.…”

Section: Resultssupporting

confidence: 66%

“…Influence of other initial conditions, like initial rotational and vibrational states of HOD molecule, on dissociation dynamics of HOD 2+ is yet to understand. Previous studies − showed that weak-field unimolecular photodissociation dynamics of HOD strongly depends on the initial vibrational state of HOD molecule. In this article, we would like to answer the question: Does the dissociation dynamics of HOD 2+ depend on the initial vibrational state of HOD molecule as in the case of HOD photodissociation?…”

Section: Introductionmentioning

confidence: 99%

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Effect of Vibrational Pre-Excitation on the Dissociation Dynamics of HOD²⁺

Dey

Tiwari

2016

J. Phys. Chem. A

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Preferential breaking of chemical bonds using few-cycle, intense laser pulse to obtain desired products offer a formidable challenge in understanding ultrafast chemical reactivity. In a recent study [J. Chem. Phys. 2015, 143, 244310], it was found that carrier-envelope phase influences the bond-selective fragmentation in HOD with up to 3-fold enhancement. We present a detailed theoretical study to understand the influence of initial vibrational states governing the dissociation dynamics. We have carried out a time-dependent quantum mechanical wave packet study on the ground electronic state (X̃ (3)B1) of HOD(2+). Analytical potential energy surface for the ground electronic states of both the neutral molecule and dication has been developed at multireference configuration interaction level of theory with aug-cc-pVQZ basis set. Branching ratio is computed from the accumulated flux in H(+) + OD(+) and D(+) + OH(+) dissociation channels. Our investigation demonstrate a strong dependency on the initial conditions, and thereby preferential cleavage of bonds can be achieved. We have also compared our results with experimental and other theoretical studies.

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Section: Resultssupporting

confidence: 66%

Section: Introductionmentioning

confidence: 99%

Effect of Vibrational Pre-Excitation on the Dissociation Dynamics of HOD²⁺

Dey

Tiwari

2016

J. Phys. Chem. A

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“…[90] and need not be repeated here. Equivalently, these matrix elements can also be obtained with MCTDH time propagation [91][92][93][94][95]97]. The phase factors containing n in Eqs.…”

Section: Theorymentioning

confidence: 99%

“…[87], which however treats the vibronic dynamics in the neutral manifold. Finally, treatments of Patchkovskii and Schuurman [90], Varandas et al [91][92][93][94][95], and Arnold et al [97] fully treat cationic vibronic dynamics, but neglect neutral dynamics and their coupling to the HHG process.…”

Section: Theorymentioning

confidence: 99%

Full-dimensional treatment of short-time vibronic dynamics in a molecular high-order-harmonic-generation process in methane

Patchkovskii

Schuurman

2017

Phys. Rev. A

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We present derivation and implementation of the multiconfigurational strong-field approximation with Gaussian nuclear wave packets (MC-SFA-GWP)-a version of the molecular strong-field approximation which treats all electronic and nuclear degrees of freedom, including their correlations, quantum mechanically. The technique allows realistic simulation of high-order-harmonic emission in polyatomic molecules without invoking reduced-dimensionality models for the nuclear motion or the electronic structure. We use MC-SFA-GWP to model isotope effects in high-order-harmonic-generation (HHG) spectroscopy of methane. The HHG emission in this molecule transiently involves the strongly vibronically coupled 2 F 2 electronic state of the CH 4 + cation. We show that the isotopic HHG ratio in methane contains signatures of (a) field-free vibronic dynamics at the conical intersection (CI); (b) resonant features in the recombination cross sections; (c) laser-driven bound-state dynamics; as well as (d) the well-known short-time Gaussian decay of the emission. We assign the intrinsic vibronic feature (a) to a relatively long-lived ( 4 fs) vibronic wave packet of the singly excited ν 4 (t 2 ) and ν 2 (e) vibrational modes, strongly coupled to the components of the 2 F 2 electronic state. We demonstrate that these physical effects differ in their dependence on the wavelength, intensity, and duration of the driving pulse, allowing them to be disentangled. We thus show that HHG spectroscopy provides a versatile tool for exploring both conical intersections and resonant features in photorecombination matrix elements in the regime not easily accessible with other techniques.

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“…Molecular isomerization, [14][15][16] and in particular intramolecular hydrogen migration, 17,18 is one of the molecular processes that can be affected under asymmetric laser irradiation. Due to the light mass of the H, its migration along the molecular skeleton can be fast and completed within a few fs 19 i.e. within the pulse duration.…”

Section: Introductionmentioning

confidence: 99%